CN109776032A

CN109776032A - Geopolymer resin materials, geopolymer materials and materials prepared therefrom

Info

Publication number: CN109776032A
Application number: CN201811333450.7A
Authority: CN
Inventors: D-K.西奥; D.梅德佩利; D.拉德; M.梅斯加
Original assignee: Arizona State University ASU
Current assignee: Arizona State University ASU
Priority date: 2011-09-21
Filing date: 2012-09-21
Publication date: 2019-05-21
Also published as: EP2758355B1; US9296654B2; EP2758355A2; WO2013044016A3; KR20140069200A; US9862644B2; US20140342156A1; KR102060844B1; EP2758355A4; WO2013044016A2; CN103946181A; US20160168032A1

Abstract

The present invention relates to geopolymer resin material, geopolymer and materials prepared therefrom.By making the first material contact and remove at least part fluid with fluid to obtain product, the first material of cause forms product, and first material includes geopolymer resin material, geopolymer resin or combinations thereof.It, can be by the initial geopolymer resin material of heating and/or aging to obtain the first material, to form the first material before contacting the first material with fluid.In some cases, contact of first material with fluid crushes or divides the first material (for example, as to the response contacted with fluid and in the case where no external mechanical stress), to form the particle that external dimensions is 1nm to 2cm.

Description

Geopolymer resin material, geopolymer and material prepared therefrom

The application is application No. is 201280056993.3, and the applying date is on September 21st, 2012, entitled " gather The divisional application of the Chinese invention patent application of polymer resin material, geopolymer and material prepared therefrom ".

The explanation of GOVERNMENT INTERESTS

This research work is to inspire solar energy fuel production (Bio-Inspired Solar Fuel by biology Production) center is supported, it is by U.S. Department of Energy, scientific office, base that biology, which inspires solar energy fuel production center, Plinth energy science office (U.S.Department of Energy, Office of Science, Office of Basic Energy Sciences) with energy forward position research center (the Energy Frontier of fund DE-SC0001016 subsidy Research Center).Government has certain rights in the invention.

Cross reference to related applications

What the U. S. application 61/537,378 and 2012 year submitted for 21st this application claims September in 2011 was submitted on May 22, The priority of U. S. application 61/650,338, by the two applications by reference to being fully incorporated the application.

Technical field

It is formed the present invention relates to geopolymer (geopolymer) resin material, geopolymer and by them Material.

Background of invention

Geopolymer resin used in this application is by being dissolved in selected metal precursor in aqueous slkali come shape At aqueous mixture.It is tied, is come by the dissolution and polycondensation reaction that mediate alkali of the aluminosilicate in water-bearing media Form certain geopolymer resins.Other geopolymer resins are for example, by superphosphate precursor solution and alkalinous metal Acid-Base between oxide precursor reacts to be formed.Geopolymer is formed by solidification geopolymer resin.Geopolymer Be usually directed to multiple terms, including low temperature alumina silicate glass, alkali activate cement, cement (geocement), alkali bonding Ceramics (alkali-bonded ceramic), inorganic polymer concrete and infiltration ceramics.

Summary of the invention

On the one hand, it contacts the first material with fluid, removes at least part fluid, obtain product.First material packet Include geopolymer resin material, geopolymer, or combinations thereof.

Implementation may include one or more of following features.For example, can heat and/or ground that aging is initial gathers Polymer resin material, obtains the first material, contacts the first material with fluid.Contact of first material with fluid can be with (break up) or division (disintegrate) first material are crushed, to form particle.That is, as contacting with fluid Response and in the case where no external mechanical stress, the first material can occur to crush or divide.

In some cases, the first material includes one or more organic compounds, and respective molecular weight is less than 1000g/ Mol (for example, the first material does not include the organic compound that molecular weight is 1000g/mol or more, such as organic polymer).The One material may include vegetable oil, vegetable oil (plant oil), animal oil, abandoned vegetable oil, discarded animal oil, fat, life Object diesel oil, fatty acid, lipid, ester, carboxylic acid, or combinations thereof.First material can be monolith.In an example, the first material Material includes geopolymer resin material, and fluid and the first material are miscible, and product is uniform mixture.In another example, First material includes geopolymer resin material, and product includes different geopolymer resin material.In a further example, One material includes geopolymer resin material, fluid and the first material immiscible, and product includes different geopolymer resin Material.In some cases, the first material includes geopolymer resin material, and product includes geopolymer.

In an example, the first material includes geopolymer resin material, and geopolymer resin material includes and alkali soluble The organic compound of liquid reaction, to prepare the carboxylic acid ion that one or more molecular weight are less than 400g/mol.In another example In, the first material includes geopolymer resin material, and geopolymer resin material includes the carboxylic acid that molecular weight is less than 400g/mol Radical ion.Contact of first material with fluid may include being transferred to carboxylic acid ion in fluid from the first material, to increase Add carboxylic acid ion concentration in a fluid.

Product can be the nanosostructured zeolite in the form of particle, particle agglomeration and/or particle aggregate.At certain In a little situations, the external dimensions of at least 50% particle is 1nm to 100nm.The zeolite of nanostructure can have at one or In multiple sizes it is the internal structure or surface texture of 1nm to 100nm, or is greater than 60m²/cm³The outside based on volume compare table Area.Product can be it is porous, wherein more than half holes is micropore, mesoporous or macropore.In some cases, product is more Grade pore structure.

Fluid can be water or aqueous solution.In some cases, fluid includes organic solvent, dissolution, dispersion or outstanding Floating species, or both.In some cases, fluid includes steam.

Therefore, it has been described that specific embodiment.The embodiment party can be carried out based on described and explanation content Variation, modification and the enhancement of formula and other embodiment.Furthermore, it is possible in conjunction with one of one or more embodiments or Multiple features.One or more implementations and multiple features and aspect are illustrated in the following drawings, description and claims Details.

Detailed description of the invention

Figure 1A -1E is the flow chart for showing the method by geopolymer resin material and geopolymer forming material.

Fig. 2A and 2B respectively illustrates transmission electron microscope (TEM) image and scanning electricity of product in example 2 Sub- microscope (SEM) image.

Fig. 3 A, 3B and 3C show the x-ray diffractogram of powder sample of the sample in embodiment 6.Fig. 3 D is with octahedral boiling The simulation pattern of the NaX zeolite of stone-type (FAU) structure.

Fig. 4 shows the x-ray diffractogram of powder sample of the sample in embodiment 7 and the simulation pattern of sodalite (SOD).

Fig. 5 A, 5B, 5C and 5D respectively illustrate the nitrogen adsorption isotherm of sample, Barret- in embodiment 8 Joyner-Halenda (BJH) pore size distribution, scanning electron micrographs (SEM) and powder X-ray x ray diffraction pattern (together with The simulation pattern of NaX zeolite (FAU) and anatase is together).

Fig. 6 shows the x-ray diffractogram of powder sample of the sample in embodiment 9 and has faujasite-type (FAU) structure NaX zeolite simulation pattern.

Fig. 7 shows that the x-ray diffractogram of powder sample of the sample in embodiment 10 is tied with having faujasite-type (FAU) The simulation pattern of the NaX zeolite of structure.

Fig. 8 A, 8B, 8C, 8D and 8E respectively illustrate the Barret-Joyner-Halenda of the sample in embodiment 11 (BJH) pore size distribution, nitrogen adsorption isotherm, x-ray diffractogram of powder sample are (together with the simulation pattern of NaX zeolite (FAU) Together), scanning electron micrographs (SEM) and transmission electron micrograph (TEM).

Fig. 9 shows that the x-ray diffractogram of powder sample of the sample in embodiment 12 is tied with having faujasite-type (FAU) The simulation pattern of the NaX zeolite of structure.

Figure 10 is shown in embodiment 14 in the x-ray diffractogram of powder sample of 85 DEG C of dry products.

Figure 11 is shown in embodiment 17 in the x-ray diffractogram of powder sample of 85 DEG C of dry products.

Figure 12 A and 12B respectively illustrate transmission electron microscope (TEM) image and the scanning of the product in embodiment 20 Electron microscope (SEM) image.

Figure 13 shows thermogravimetric analysis (TGA) curve (solid line) of the product in embodiment 22 and does not carry out alcohol treatment And thermogravimetric analysis (TGA) curve (dotted line) of the geopolymer prepared.

Figure 14 A shows thermogravimetric analysis (TGA) curve of the product in embodiment 23.Figure 14 B is shown in embodiment 23 The Fourier of fourier-transform infrared (FT-IR) spectrum (lower part) of middle product and the geopolymer for not using glycerol to prepare Infrared (FT-IR) spectrum (top) of leaf transformation.

Figure 15 is Barret-Joyner-Halenda (BJH) the De contamination pore size point of first sample in embodiment 24 Cloth.

Figure 16 is the nitrogen adsorption isotherm of first sample in embodiment 24.

Figure 17 is Barret-Joyner-Halenda (BJH) the De contamination pore size point of second sample in embodiment 24 Cloth.

Figure 18 is the nitrogen adsorption isotherm of second sample in embodiment 24.

Figure 19 is the scanning electron micrographs (SEM) of the sample in embodiment 25.

Figure 20 is Barret-Joyner-Halenda (BJH) the De contamination pore size point of second sample in embodiment 25 Cloth.

Figure 21 is the nitrogen adsorption isotherm of second sample in embodiment 25.

Figure 22 is the diffraction of the x-ray diffractogram of powder sample of the sample in embodiment 25 Yu the simulation of NaX zeolite (FAU) Pattern.

Figure 23 is the diffraction of the x-ray diffractogram of powder sample of the sample in embodiment 27 Yu the simulation of NaX zeolite (FAU) Pattern.

Figure 24 is the scanning electron micrographs (SEM) of the sample in embodiment 39.

Figure 25 is Barret-Joyner-Halenda (BJH) the De contamination pore size point of second sample in embodiment 39 Cloth.

Figure 26 is the nitrogen adsorption isotherm of second sample in embodiment 39.

Figure 27 is Barret-Joyner-Halenda (BJH) the De contamination pore size point of second sample in embodiment 40 Cloth.

Figure 28 is the nitrogen adsorption isotherm of second sample in embodiment 40.

Figure 29 is Barret-Joyner-Halenda (BJH) the De contamination pore size point of second sample in embodiment 41 Cloth.

Figure 30 is the nitrogen adsorption isotherm of second sample in embodiment 41.

It is described in detail

Geopolymer resin can be prepared in many ways.In an example, by metal oxide precursor through acid- The dissolution of alkali reaction and the precipitating of subsequent phosphate or silicophosphate, to prepare geopolymer resin.In another example, It is tied by the dissolution and precipitation reaction that mediate the alkali of silicate or aluminosilicate precursors in water-bearing media, to make Standby geopolymer resin.It can be by making metakaolin (metakaolin) or metakaolin (metakaolinite) and phosphoric acid Reaction, to prepare the geopolymer resin including silicoaluminophosphate.It can be by keeping clay material and alkaline solution or acidity molten Liquid reaction, to form another geopolymer resin.In other examples, keeping metakaolin and metakaolin and aqueous slkali anti- Geopolymer resin should be formed.Geopolymer resin generally includes water and dissolution, dispersion or suspension inorganic species, The geopolymer resin can appear to be homogeneous when visual inspection.Geopolymer resin, which is described in, to be mentioned on June 1st, 2012 The U.S. Patent application 13/513,220 of friendship, by it by reference to being fully incorporated in the application.

Solidification geopolymer resin can produce geopolymer gel or geopolymer.The temperature that curing method can occur Degree includes such as environment temperature (e.g., 15 DEG C -35 DEG C) and high temperature (e.g., 40 DEG C -90 DEG C).Suggest 2007 according to IUPAC (" the Definitions of Terms Relating to the Structure and Processing of such as J.Alem á n Sols,Gels, Networks,and Inorganic–Organic HybridMaterials,” Pure and Applied Chemistry, 2007,79,1801), " solidification " is the polymer, so by prepolymer or polymer conversion at high molecular weight It is transformed into the chemical process into network afterwards.The chemistry mixed with chemical curing agent may be needed or may not be needed by introducing Reaction, to realize solidification.Suggest 2007 according to IUPAC, " gel " is the non-streaming for expanding it by fluid in its whole volume Body gel networks or polymer network.Geopolymer gel contains inorganic colloid or polymer network, as by inorganic precursor The network that polycondensation is formed.In some cases, geopolymer is that at least part liquid (e.g., water) has been had lost from gel Geopolymer gel.In some cases, solidifying can lose along at least part of liquid and (e.g., pass through evaporation). " geopolymer " used in this application is often referred to geopolymer gel, geopolymer, geopolymer gel composite wood Material, geopolymer composite material or their combination.

Under certain conditions, using certain compositions or in the presence of, geopolymer Resin can be not fully cured (e.g., partially cured) or not be solidified (such as uncured) completely.Gather on the ground being uncured or partially cured Polymer resin is not contained in the inorganic colloid or polymer network for expanding it by fluid in its whole volume.In uncured or portion Divide the inorganic network structure in cured geopolymer resin to can be separation, or can be demi-inflation in a fluid. Geopolymer resin material can contain isolated particle, aggregate, aggregation or their combination.Used in this application It is multiple that " geopolymer resin material " is often referred to geopolymer resin, partially cured geopolymer resin, geopolymer resin Condensation material, partially cured geopolymer resin composite materials or their combination.Geopolymer resin material can be liquid Body, semiliquid, semisolid or solid can appear to be heterogeneous when visually inspecting.When in the feelings without gel-forming When removing fluid (e.g., the water) in (e.g., passing through evaporation) geopolymer resin material under condition, solid geopolymer can be obtained Resin material.Water is removed from the part in geopolymer resin material can produce paste.When stirring or be shaken to mixed geopolymer tree When rouge material, geopolymer resin material can become fluid.

It can occur in short curing time (a few hours or one day, such as) and/or low solidification temperature (for example, in room temperature) Geopolymer resin or geopolymer resin composite materials it is partially cured.In some cases, when a large amount of water and/or alkali When being present in geopolymer resin or geopolymer resin composite materials, or when organic component is present in geopolymer resin Or when in geopolymer resin composite materials, occur partially cured.In some cases, partially cured can be along with liquid From at least partly loss (e.g., passing through evaporation) in geopolymer resin or geopolymer resin composite materials.High temperature usually adds Speed solidification.In some cases, the transformation temperature during being cured or partially cured.In some cases, solid in solidification or part Geopolymer resin or geopolymer resin composite materials are maintained at specific temperature (for example, room temperature) a period of time before change (that is, aging).In some cases, geopolymer resin or geopolymer resin composite materials are being cured or partially cured it Aging afterwards.

It can be by the way that multiple components be added in geopolymer resin, to prepare geopolymer resin composite materials.Ground The solidification of fluoropolymer resin composite material can produce geopolymer composite material (multicomponent geopolymer).Gather to multicomponent It closes object to be described in United States Patent (USP) 5,244,726 and United States Patent (USP) 7,771,686, the two patents is incorporated by reference into this In application.The example of the component of multicomponent geopolymer or geopolymer composite material includes nano particle, nano material, nothing Machine particle, organic granular, biomaterial, molecule, cation, anion etc..Other components include, for example, structure directing agent or Hole template, such as quaternary ammonium ion, cyclodextrin, surfactant, glucose, starch, cellulose fibre.Other groups of subpackages It includes, for example, the organic monomer miscible with water, oligomer, macromonomer, polymer；Can hydrolyze and with geopolymer tree The compound of rouge condensation, such as organosilan, organosiloxane, Organoaluminoxy alkane and organo metallic oxide；Inorganic compound, Such as water-soluble metal-organic complex and inorganic metal compound；The miscible fluid with water, such as glycerol, ethylene glycol, polynary Alcohol, alcohol, acetone, tetrahydrofuran, dimethyl sulfoxide and N-Methyl pyrrolidone；Gas is generated when contacting with geopolymer resin The substance (for example, hydrogen peroxide, aluminum metal or silicon ash) of body.In some cases, component in addition includes vegetable oil, plant Oil, animal oil, abandoned vegetable oil, discarded animal oil, fat, biodiesel, fatty acid, lipid, ester, carboxylic acid, based on petroleum Oil, or combinations thereof.Vegetable oil, vegetable oil, animal oil, abandoned vegetable oil, discarded animal oil, fat, biodiesel, fatty acid, Lipid, ester or carboxylic acid can prepare carboxylate anion with geopolymer resin reaction.

The source of silicon in geopolymer and geopolymer resin material includes, for example, vapor deposition titanium dioxide Silicon, rice husk (rice husk), rice hull ash, silicon ash, silicate, aluminosilicate, organosilan, clay, mineral, metakaolin, Calcined clay, activated clay, flying dust, clinker, volcanic ash, burning multi-purpose waste material (incinerated utility Waste), industrial by-products, glass powder, red mud etc..The source of aluminium may include in geopolymer and geopolymer resin, For example, aluminium oxide, aluminate, aluminium salt, Organoaluminoxy alkane, clay, mineral, metakaolin, calcined clay, activated clay, fly Ash, clinker, volcanic ash, the multi-purpose waste material of burning, industrial by-products, glass powder, red mud etc..In geopolymer and geopolymer The source of phosphorus may include phosphoric acid, phosphate, hydrophosphate, organo-phosphine oxide etc. in resin.Some geopolymers or ground polymerization Resin includes one or more metals in ion or simple substance form, as Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Ra、B、Al、Ga、In、Tl、 Si、Ge、Sn、Pb、P、As、Sb、Bi、S、Se、Te、Po、Ti、Zr、Hf、V、Nb、 Ta、Cr、Mo、 W、Mn、Tc、Re、Fe、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt、 Cu、Ag、Au、Zn、Cd、Hg、Sc、Y、Lu、La、Ce、Pr、Nd、 Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Th, U, Pu or their any combination.Geopolymer and geopolymer are compound The preparation of material is described in such as W.M.Kriven, " Inorganic Polysialates or ' Geopolymers ', " American Ceramic Society Bulletin,2010,89,31；A.S.Wagh, "Chemically Bonded Phosphate Ceramics–A Novel Class of Geopolymers,”Ceramic Transactions 2005, 165,101；The chapter 1 of the written Geopolymer:Chemistry and Applications " of J.Davidovits； D.S.Perera etc., " Relative Strengths of Phosphoric Acid-Reacted and Alkali- Reacted Metakaolin Materials ", Journal of Material Science2008,43,6562, will own Document is incorporated herein by reference.

With reference to Figure 1A, the method 100 for preparing material includes making geopolymer resin material or geopolymer in 102 Material contacts (for example, mixture or their combination of the mixture of liquid, liquid, gas, gas) with fluid.It can press Contracting the fluid or makes the fluid under stress.In some cases, fluid includes steam.Geopolymer resin material can wrap Include the particle of geopolymer or geopolymer composite material.Geopolymer resin material can be liquid, semiliquid, paste, half Solid or solid (including soft solid or semi-rigid solid).

In some cases, geopolymer has crack and/or micro-crack in its entity.In geopolymer material Material can form crack and/or micro-crack during being formed.In different formation condition (including humidity level, curing time and temperature Degree) under, the degree and shape of crack and/or micro-crack are alterable.Pass through the leaching of geopolymer or burn into acid or alkali Chemical erosion, thermal shock, the processing of fluid etc., crack and/or micro-crack can be formed.It is applied to geopolymer entity In hole wall on capillary pressure can promote the formation of crack and/or micro-crack.

Fluid in 102 may include water or aqueous solution (for example, acid solution, alkaline solution or buffer solution) or Organic solvent (for example, alcohol, such as methanol and ethyl alcohol) or organic solution (such as iron chloride (FeCl₃·6H₂O) in methyl alcohol molten Liquid).When fluid includes organic solvent, organic solvent can be it is volatile, and when fluid and geopolymer resin material or Geopolymer can be evaporated when contacting.Organic solvent can be more more sticky than water.In some cases, fluid with Geopolymer resin material is unmixing, and fluid is miscible with water, or both occur.In some cases, fluid is aqueous or has The solution or mixture of machine, including dissolution, dispersion or suspension species, the species include molecule, metal precursor, gold Category, semiconductor, insulator, monomer, oligomer, polymer, macromonomer, ion, salt, biomaterial, surfactant, Cluster (clusters), nano particle, nano material, particle, fiber, filler, inorganic particle, organic granular, inorganic compound, Organic compound, solvate molecule, cation, anion, organic solvent, lotion, fiber, foams, porous material, quantum Point, magnetic material and other (including structure directing agent or hole template such as quaternary ammonium ion, cyclodextrin, glucose, starch, fibers Cellulose fiber, surfactant etc. or their combination).Suitable surfactant includes such as polymerization or polymerizable table Face activating agent；Cationic, anionic or nonionic surface active agent etc..One or more components in a fluid can With with one of the inorganic or organic component of geopolymer resin material or geopolymer or it is a variety of react (for example, from Sub-key is closed or covalent bonding).In some implementations, it can be connect in fluid and geopolymer resin material or geopolymer These species are added in fluid after touching.

The contact of geopolymer resin material or geopolymer with fluid may include mixing, being blended, being shaken to mixed, cutting It cuts, homogenize, stirring, stirring, ultrasound and/or oscillation geopolymer resin material or geopolymer containing fluid, or Person crushes (crushing), pulverizes (pounding), grinding (grinding), grind (pulverizing), grind (milling), it is crushed (crumbling), (smashing) is crushed, smashs (mashing), compacting to pieces or develop in a fluid Geopolymer resin material or geopolymer.In some cases, geopolymer resin material or geopolymer with The contact of fluid includes polymerizeing geopolymer resin material or geopolymer leaching in a fluid or with using fluid flushing Resin material or geopolymer.

The contact of geopolymer resin material or geopolymer with fluid can increase or decrease geopolymer resin The temperature of material or geopolymer.Geopolymer resin material or geopolymer and fluid before contact can be with In different temperature.In some cases, can in room temperature, be higher than room temperature or be lower than room temperature, or when to fluid, geopolymer Resin material or geopolymer, or both when being heated or cooled, carry out geopolymer resin material or geopolymer Contact with fluid.In some cases, by condensing to fluid on geopolymer resin material or geopolymer Carry out the contact of geopolymer resin material or geopolymer with fluid among and/or or under stress.

In some cases, the contact of geopolymer resin material or geopolymer with fluid is so that fluid components One of or it is a variety of be transferred in geopolymer resin material or geopolymer, and/or make geopolymer resinous wood One of component of material or geopolymer or a variety of (e.g., water) are transferred in fluid.One of fluid components are more Kind can with one of the component of geopolymer resin material or geopolymer or a variety of react.Reaction may include, For example, acid-base neutralization or covalent linkage (for example, crosslinking).In some cases, one of fluid components or it is a variety of with ground gather One of polymer resin material or geopolymer component a variety of covalently connect.Geopolymer resin material or ground Contact of the polymer material with fluid can cause the pH of geopolymer resin material or geopolymer, viscosity or from The variation of sub- intensity.In some cases, contact acceleration or deceleration geopolymer resin of the geopolymer resin material with fluid The solidification of material.

Contact of the geopolymer resin material with fluid can produce uniform mixture.The composition of uniform mixture The composition of geopolymer resin material be can be different from (for example, being attributed at least partially dissolution, dispersion or suspension Species).In some cases, the pH relative to geopolymer resin material, dissolution, dispersion or suspension species can be with Change the pH of homogeneous mixture, so that the pH of uniform mixture is different from the pH of geopolymer resin material.

The contact of geopolymer resin material or geopolymer with fluid can produce geopolymer resin material or The non-homogeneous mixture of geopolymer and fluid.In an example, contact of the geopolymer resin material with fluid produces The drop of Radix Rehmanniae polymer resin material dispersion in a fluid.In some cases, geopolymer resin material or geopolymer Contact of the material with fluid is so that geopolymer resin material or geopolymer crush or split into particle.For example, ground gathers Polymer resin material or geopolymer can divide the reunion to form particle, particle when it is contacted with fluid (such as water) The aggregation of body and/or particle.In some cases, the size of particle is 1nm to 2cm.Division can produce dispersion or Suspended substance.In some cases, particle is mutually separated by gravity or by flocculation.External machinery can be with or without In the case where stress (for example, such as suppress in no mechanical-assisted, mix, being blended, being shaken to mixed, shearing, homogenizing, stirring, stirring, In the case where ultrasound, oscillation etc.) form particle.

In 104, it removes at least part fluid and forms the first product.It may include molten for removing at least part fluid The removal of the species of solution and/or the fluid are exchanged with another fluid.First product can (for example, on composition, pH etc.) no It is same as geopolymer resin material or geopolymer.Removing fluids may include decantation, filtering, centrifugation, drying, surpass and face Boundary is dry, freeze-drying, evaporation, dehydration, heating, pyrolysis, calcining etc..In some cases, removing fluids include passing through addition Clarifying agent, flocculant or coagulant are flocculated, are reunited, are assembled, agglomerated or are coalesced.Fluid content be can control to improve The mechanical performance (for example, compressive strength) of one product.In an example, it when the first product is monolith, selectively controls Fluid content processed reduces or avoids the crack in resulting materials.

In the method 100, the geopolymer resin material or ground in 102 can be carried out using identical or different fluid Contact of the polymer material with fluid and/or subsequent removal at least part fluid in 104 are more than primary.

In some cases, the first product is in the form of dispersion or suspended substance.In other situations, more than half amounts are removed Fluid, obtain the first product of particle or powder.Most of first product particles can be less than 2cm, 5mm, 10 microns, it is 1 micro- Rice or 100nm.Granular materials by following material composition or can may include substantially following substance: nano material or nanometer Structural material (that is, the material being made of the aggregation of particle, the aggregate of particle, and/or particle, for the material, particle With one or more external dimensions (about 50% size range more than their numbers is 1-100nm)；And/or have Size range is the internal structure or surface texture of 1-100nm in one or more sizes；And/or has and be greater than 60m²/cm³ The specific external surface area based on volume).It can be tested by such as gas absorption by the specific external surface area assessment of material and be Difference between Brunauer-Emmett-Teller (BET) surface area and specific surface area derived from micropore in material.It can be by example As t- drawing method assessment derives from the specific surface area of micropore.The example of nano structural material includes nano particle, nanometer rods, nanometer Band, nano-plates, nanometer sheet, nano wire, nanofiber and nano-porous materials.

First product can show macropore, mesoporous, micropore or their combination (that is, for example, hierarchical porous structure).The One product can have the when institute for example in X-ray, electronics and/or the neutron diffraction pattern that Bragg reflection peak is present in material Certain crystallinity of understanding.In some cases, the first product is (or including) zeolite, and such as nanosostructured zeolite is situated between and sees knot Structure zeolite or porous zeotile.In some cases, geopolymer resin material or geopolymer include zeolite component.

Zeolite is usually described as crystalline aluminosilicate, has well-regulated channel and/or basket structure, and containing preferred Micropore less than about 0.9nm.The network structure of the zeolite by share oxygen bridge SiO₄And AlO₄Tetrahedron composition.Example is that have The zeolite structured zeolite of five silicon rings, especially by X-ray analysis be attributed to ABW, AGO, AEI, AEL, AEN, AET, AFG, AFI、AFN、AFO、AFR、 AFS、AFT、AFX、AFY、AHT、ANA、APC、APD、AST、ATN、ATO、 ATS、ATT、ATY、 AWO、AWW、BEA、BIK、BOG、BPH、BRE、CAN、 CAS、CFI、CGF、CGS、CHA、CHI、CLO、CON、CZP、DAC、DDR、 DFO、DFT、DOH、DON、EAB、EDI、EMT、EPI、ERI、ESY、EUO、FAU、 FER、GIS、GME、GOO、HEU、IFR、ISY、 ITE、JBW、KFI、LAU、LEV、 LIO、LOS、LOY、LTA、LTL、LTN、MAZ、MEI、MEL、MEP、MER、 MFI、MFS、 MON、MOR、MSO、MTF、MTN、MTT、MTW、MWW、NAT、 NES、NON、OFF、OSI、PAR、PAU、PHI、RHO、RON、RSN、 RTE、RTH、 RUT、SAO、SAT、SBE、SBS、SBT、SFF、SGT、SOD、STF、STI、STT、 TER、THO、TON、TSC、 The type of VET, VFI, VNI, VSY, WIE, WEN, YUG and ZON structure and the mixed structure of two or more in them. The known zeolite that aluminium is wherein not present, it is also known that a part of the Si (IV) in its lattice silicate is by the titanium as Ti (IV) Instead of some zeolites, such as titanium zeolite.Some zeolitic materials can also include other elements, as aluminium, zirconium, tin, iron, cobalt, Nickel, gallium, germanium, boron or a small amount of fluorine.Part or all of the titanium of zeolite can by vanadium, zirconium, chromium or niobium or two in them kinds or More kinds of mixtures replace.Some examples of zeolite are AlO of the network structure by shared oxygen bridge₄And PO₄Tetrahedron composition Aluminate or phosphate.

In 106, optionally processing derives from 104 the first product, obtains the second product.Handling the first product can wrap Include extraction, dipping, etching, melting, distillation, dissolution, decomposition, evaporation, heating, hydro-thermal process, solvent heat treatment, at ion heat Reason, burning, calcining, etching etc..Heat the first product can cause the dehydration of material, decomposition, pyrolysis, carbon-thermal reduction, burning or Crystallization.In some cases, heating material may make at least part hole (when it is present) to close and cannot be introduced into.Some In situation, heating material may make at least part hole (when it is present) to collapse.Handling the first product can lead to the shifting of component Remove, replace, being added (for example, making components precipitate or deposition in a some holes of the first product, the first product is injected the additive into, Form geopolymer composite material etc.), or change crystallinity or porosity to form the second product.Handle its of the first product Its example includes ion-exchange, double decomposition etc..

It is more than primary, the second product of change that optional processing 106 can be carried out with identical or different processing method.? In one example, the second product can be processed, obtains composite material (for example, by making the first product and additive (including gas Body, liquid, solid or their combination) contact；By inorganic particle, organic granular, inorganic compound, organic compound, biology Material, polymer, carbon, metal etc. or their combination inject the second product).Handling the second product may include change second Chemical composition, chemical structure, microstructure form or the pore morphology of product.

The method 200 being shown in Figure 1B is the example of method 100.In 202, geopolymer resin material and liquid Contact produce dispersion or suspended substance.In some cases, liquid includes dissolution, dispersion or suspension species.Liquid can To be water or organic solvent, such as methanol.Liquid can be aqueous solution (for example, cetyl trimethylammonium bromide (CTAB) is water-soluble Liquid) or organic solution (for example, CTAB solution in ethanol).In 204, at least part is removed (for example, at least half Or more than half amounts) liquid generate the first product of particulate form.In some cases, the first product is in the form of powder.Particle or powder It end can be in the form of dispersion or suspended substance.More than half particles can be less than 1000 microns, less than 1 micron or be less than 100nm.In optional 206, the first product is handled, the second product is obtained.

The method 300 being shown in Fig. 1 C is the example of method 100.In step 302, geopolymer resin material and liquid The contact of body generates uniform mixture, and the composition and/or pH of the mixture are different from the composition of geopolymer resin material And/or pH.Liquid may include dissolution, dispersion or suspension species.Liquid can be water, acid solution (for example, phosphorus Acid) or alkaline (or alkali) solution (sodium hydroxide).In some cases, liquid is pH buffer, contains biomaterial.? In certain situations, liquid is viscous liquid, such as glycerol or ethylene glycol, and may include additive, such as carbon black.In 304, from The liquid that at least part (for example, at least half or more than half amounts) is removed in uniform mixture can generate the first product.It removes At least part liquid may include pyrolysis or calcining.In instances, when being heated in the limited environment of oxygen, containing gather Glycerol in the homogeneous mixture of polymer resin material loses the hydrogen, carbon and oxygen of more than half amounts, to become graphite material.? In another example, the mixture of the glycerol containing carbon particle is mixed into geopolymer resin material, heat the mixture from And it is pyrolyzed glycerol.Method 300 may include 306, wherein handling the first product to obtain the second product.

The method 400 being shown in Fig. 1 D is the example of method 100.In 402, the first geopolymer resin material and liquid The contact of body changes the composition and/or pH of the first geopolymer resin material.Liquid or solvent can be organic liquid, such as second Alcohol or tetrahydrofuran.In some cases, liquid and the first geopolymer resin material are unmixing, or with the first geopolymer Resin material is unmixing, but miscible with water.Contact of the first geopolymer resin material with liquid can change the first polymerization The viscosity of resin material.In instances, the first geopolymer resin material and the contact of liquid (for example, ethyl alcohol) are from first It is extracted water in geopolymer resin material, and has obtained heterogeneous mixture.Can make geopolymer resin material with Liquid (including dissolution, dispersion or suspension species) contact, to change the composition of the first geopolymer resin material And/or pH.In some cases, contact of the first geopolymer resin material with liquid causes geopolymer resin material And/or the variation in the ionic strength of liquid, or cause the cured acceleration or deceleration of geopolymer resin material.

In 404, the liquid of (for example, a part, half, more than half amounts) is removed, forms the second geopolymer resin Material.The composition and/or pH of second geopolymer resin material be different from the first geopolymer resin material composition and/or pH.Liquid can be removed by decantation, filtering, drying, freeze-drying, evaporation, dehydration, heating, pyrolysis or calcining.406 In can solidify the second geopolymer resin material, form the first geopolymer.It can handle the first ground in 408 to gather Object material is closed, the second geopolymer is formed.

The method 500 being shown in Fig. 1 E is the example of method 100.In 502, make to include the first of geopolymer Material is contacted with fluid.Contact of first material with fluid can crush or divide the first material.When the first material connects with fluid When touching, the first material can pass through the fluid-absorbent to a certain extent of hole, crack or the micro-crack in the first material entities.? In some cases, the fluid of absorption or its meniscus can be in hole wall, sides of fracture and/or the micro-cracks in the first material entities Apply capillary pressure on wall, thus the crushing or division of the first material can be caused.In some cases, the fluid of absorption Hole wall, sides of fracture and/or micro-crack wall can be weakened by aquation, etching, dissolution etc., thus can lead to first The crushing or division of material.By the temperature of fluid, pressure, content and/or composition and/or the shape of the first material can be passed through Shape, size, form, composition and/or preparation condition come influence crush or divide degree.The temperature of fluid, pressure can be passed through Power, content and/or composition and/or influenced by the shape of the first material, size, form, composition and/or preparation condition by Crush or divide number, form and the size of the particle generated.In 504, at least part fluid is removed to obtain the first production Product.In optional 506, the first product is handled to obtain the second product.

Although being described in a particular order, aforesaid operations can be carried out in a different order.Furthermore, it is possible to One or more of operation is omitted, or other operation can be added.Datail description about method is in figure.1B-1E is answered It is interpreted as that Figure 1A is described.

Particle, compound and material described herein can be to chemical substance, biomaterial, electric field, magnetic field, temperature Degree, pressure, electromagnetic wave, mechanical force or their combination make a response.Particle, compound and material can be used in many ways Material, the mode include but is not limited to be used as adsorbent, adsorbent, nano-reactor, nanometre glue, nano container, nano combined Object, catalyst, catalyst carrier, oxidant, reducing agent, filter medium, chromatographic media, ion exchange material, separation material, Magneto separate material, film, gas/liquid/fuel storage material, electrode, sensor, electricity material, electronic material, magnetic material Material, microwave absorption, microwave-assisted heating material, biologic implant, structural reinforcement material, construction material, solar energy collecting Device, solar cell module, insulating materials, heat-barrier material, sound insulating material, fire retardant, coating thickener, disappears at supercapacitor Photo etching, packaging material, refractory material, additive, ink-jet paint, porous adhesive, porous aggregate, ion conductor, biological respinse Device, culture medium, culture carrier (culture supports), bone alternate material, active battery components, battery separator (battery separators), calorifics composite material (such as it is injected with Thermal energy storage material, phase transition compound, heat chemistry energy The porous geopolymer of storage material or magneto-caloric material), toxin removal material, chemicals removal material, waste material removal material, Nuisance removes material, chemical decontaminants, bioactivity detergent, smell-removing material, the peace and quiet material of oil slick, arsenic removal material, a huge sum of money Belong to removal material, nuke rubbish removes material, high energy material, evaporative freezing device/heater, fragrance release material (aroma Delivery materials), smell releasable material (flavor delivery materials), drug release material, disappear Kill microbial inoculum releasable material (sanitizer delivery materials), herbicide releasable material, fungicide release material Material, farm chemical release material, insecticide releasable material, nutrient for plants releasable material, fertilizer, plant growth medium, greening room Topping material (green roof materials), water planting mounting medium (hydroponics support media), encapsulating material Material, animal nutrient releasable material, human nutrition element releasable material, water purified material, soil curing material, wetting agent, water suction Material (water absorption materials), catchments at water adsorbent material (water adsorption materials) Material (water collection materials), water-keeping material, humidity control material, pet litter absorbing material (pet Litter absorption materials), vapor-adsorbing material, gas adsorption material, oily adsorbent material, oil extract material Material, algal oil superminiature cultivate material (algae oil nanofarming materials), selective solid phase extractions material, Desiccant, support material (proppant materials), hemostat etc..Particle, compound and material described herein Material also is used as preparing the template or mask of porous material (including porous polymer and porous ceramics).

The following example is provided to be illustrated.Those skilled in the art will appreciate that the skill disclosed in the following example Art is considered illustrative.However, according to the application, those skilled in the art will recognize that in disclosed specific implementation A variety of variations can be carried out in mode, without departing from the spirit and scope of the application.

Embodiment

Embodiment 1 illustrates the implementation of method 200, wherein by mixedly fluoropolymer resin and water, then passing through removal Water prepares particle.Embodiment 2 illustrates that the another of method 200 is implemented, wherein by using cetyl trimethyl is included Ammonium bromide (CTAB), cationic surfactant aqueous solution prepare particle.Embodiment 3 is similar to embodiment 2, but makes Use metakaolinIt is mixed using the stirring of different types of blender with different rates instead of metakaolin Polymer solution.Embodiment 4 illustrates that the another of method 200 is implemented, wherein by using cetyl trimethyl bromination is included The aqueous solution of ammonium (CTAB), cationic surfactant, then by purifying and particle dispersion in water being concentrated, to make The particle dispersion of standby viscosity.Embodiment 5 illustrates that the another of method 200 is implemented, wherein by using H₃PO₄Aqueous solution comes Prepare particle.In 206, particle or dusty material are handled to form new material.

Embodiment 6 illustrates that the another of method 200 is implemented, wherein by soft or semi-rigid geopolymer resinous wood Material is under water, and with being mildly shaken to mixed, it splits into the particle being dispersed in water.The particle has faujasite-type (FAU) Structure (zeolite).Embodiment 7 is similar to embodiment 6, but geopolymer resin material is solid, later when under water Part occurs to divide.The particle has sodalite type (SOD) structure (zeolite).

Embodiment 8 is similar to embodiment 6, but by room temperature will mushily polymer resin material it is under water, with Afterwards for several times (so that the pH of particle dispersion becomes close to 7) by washing paste, to prepare particle.Gained particle is shown Faujasite-type (FAU) structure, and contain other nano-pore in particle entities.

Embodiment 9 illustrates that the another of method 200 is implemented, wherein passing through mixedly fluoropolymer resin and canola oil (canola oil), then by incompletely or partly solidified resin, to prepare the geopolymer in soft solid form Resin material.The solid is easy to broken with record book in accordion form.In the hot water by the leaching of geopolymer resin material, wherein it splits at any time Particle.The particle shows faujasite-type (FAU) structure, and contains other nano-pore in particle entities.Embodiment 10 Being similar to embodiment 9 with 11, still geopolymer resin has different chemical compositions.Embodiment 12 is similar to embodiment 9- 11, but abandoned vegetable oil is used to replace canola oil.Embodiment 24 illustrates a kind of implementation of method 200, wherein passing through place The nominal Na:Al:Si atomic ratio of reason in water prepares particle for the geopolymer resin of 3:1:2, then by removing water. Embodiment 25 is similar to embodiment 24, but geopolymer resin includes canola oil as other precursor.In 42 He of embodiment In 43, flying dust is used as to the source of aluminosilicate.

Embodiment 14 illustrates the implementation of method 300, wherein aluminosilicate geopolymer resin is mixed with concentrated phosphoric acid, Prepare the homogeneous mixture that pH is about 7.Drying composite in an oven removes most of water, to obtain monolith.Implement Example 15 is similar to embodiment 14, but sulfuric acid is used to replace phosphoric acid.Embodiment 16 is similar to embodiment 14, but uses acetic acid Instead of phosphoric acid.Embodiment 17 is similar to

Embodiment 14, but include and TiO₂The concentrated phosphoric acid of nano particle premixing.Embodiment 18 illustrates method 300 another implementation, which use viscous liquids.By mixed carbon black particle and glycerol, the carbon-of viscosity is prepared first Glycerol mixture.The mixture is mixed with geopolymer resin then, is applied in glass slide using the mixture as shallow layer On.Pretreatment coating in an oven finally heats in 500 DEG C under argon gas stream, obtains conductive coating.Embodiment 19 illustrates Contact of the geopolymer resin material with liquid can repeatedly be carried out using different liquids.By aluminosilicate geopolymer resin It is mixed with concentrated phosphoric acid, obtains the homogeneous mixture that pH is about 7.Buffer solution (pH7) is added in mixture, is obtained another Uniform mixture.Embodiment 20 also illustrates the use of plurality of liquid.First by aluminosilicate geopolymer resin and dense phosphorus Acid-mixed is closed, and the homogeneous mixture that pH is about 7 is prepared.Then uniform mixture is mixed with the aqueous solution containing CTAB, thus most Particle is obtained eventually.Embodiment 21 illustrates that the another of method 300 is implemented, wherein subsequent use includes ten by using phosphoric acid The aqueous solution of six alkyl trimethyl ammonium bromides (CTAB), cationic surfactant, subsequent purifying and concentrated granular dispersion, To prepare the particle dispersion of viscosity.

Embodiment 13 illustrates a kind of implementation of method 300, but repeatedly carries out this method, forms new material.It is stirring Under, by iron chloride (FeCl in methyl alcohol₃·6H₂O) solution is mixed into geopolymer resin.Most of first during churning Alcohol evaporation is Red-brown powder paste to obtain geopolymer resin material.Canola oil is mixed into geopolymer tree In rouge material, the new geopolymer resin material of similar paste is provided.New geopolymer resinous wood is heated in an oven Material removes existing most of methanol and some water, to obtain dry another new geopolymer resin material.In argon Geopolymer resin material is further heated in 600 DEG C under air-flow, to obtain black powder.

Embodiment 22 illustrates the implementation of method 400.Geopolymer tree is shaken to mixed together with ethyl alcohol in closed container Rouge, and stand.After through Gravity Separation resin and ethyl alcohol, alcoholic supernatant is decanted.Take second place repeating the step 4 Afterwards, resin becomes more more sticky than initial resin.Then the resin material new in 110 DEG C of heating, prepares geopolymer. Embodiment 23 is similar to embodiment 22, the difference is that replacing having contained only using the geopolymer resin containing glycerol inorganic The geopolymer rouge of component.

Embodiment 26 to 34 illustrates the implementation of method 500, and wherein geopolymer resin material can have a variety of groups At, can solidify in multiple kinds of molds under numerous conditions, this affect gained geopolymer particle size and shape Shape.Embodiment 35 to 41 illustrates the implementation of method 500, and wherein geopolymer resin material contains potassium ion rather than sodium ion. In these embodiments, embodiment 40 and 41 illustrates the implementation of method 500, and wherein the temperature for the treatment of fluid affects production The form of product.

0.73g NaOH is dissolved in 0.95g deionized water by embodiment 1., and 12.22g sodium metasilicate is then added thereto (~10.6%Na₂O ,~26.5%SiO₂).The solution is stirred, until it becomes uniform with visual observations.In the solution, 6.10g metakaolin, stirring is added, until range estimation solution becomes uniformly, to prepare geopolymer resin.By 140ml deionization Water pours into geopolymer resin, and stir about 1 minute.Then homogenizer (IKA T25 number ULTRA- is used) It is homogenized the mixture about 10 minutes with 10000rpm.Once stop stirring, as be added methanol make gained particle precipitate, mistake Be filtered dry it is dry, to obtain powder-product.The dispersibility in water that the product is shown is better than the dispersibility in chloroform.It should Product shows about 18.1m²Nitrogen adsorption Brunauer-Emmett-Teller (BET) surface area of/g.

0.73g NaOH is dissolved in 0.95g deionized water by embodiment 2., and 12.22g sodium metasilicate is then added thereto (~10.6%Na₂O ,~26.5%SiO₂).The solution is stirred, until it becomes uniform with visual observations.In the solution, 6.10g metakaolin, stirring is added, until range estimation solution becomes uniformly, to prepare geopolymer resin.In individual container In, make 0.240g cetyl trimethylammonium bromide ((C₁₆H₃₃)N(CH₃)₃Br, CTAB) it is dissolved in 140ml deionized water. CTAB aqueous solution is poured into geopolymer resin, stir about 1 minute.Then homogenizer (IKA T25 number ULTRA- is used) homogenized the mixture about 10 minutes with 10000rpm.Once stopping stirring, make gained particle precipitating, mistake Be filtered dry it is dry, to obtain powder-product.The dispersibility in chloroform that the product is shown is better than dispersibility in water, this It is hydrophobic for showing the particle to a certain extent.CHN is analysis shows the material contains 2.475wt% carbon and 0.132wt% Nitrogen.The product shows about 22m²Nitrogen adsorption Brunauer-Emmett-Teller (BET) surface area of/g.It is forged at 750 DEG C After burning 10h, weight loss 9.3%.According to ICP as a result, the Na:Al:Si ratio of calcination product is 1:4.8:6.2.Fig. 2A The transmission electron microscope (TEM) and scanning electron microscope (SEM) image of product are shown with 2B.

0.73g NaOH is dissolved in 0.95g water by embodiment 3., then thereto be added 12.22g sodium metasilicate (~ 10.6%Na₂O ,~26.5%SiO₂).The solution is stirred, until it becomes uniform with visual observations.In the solution, add Enter 6.10g metakaolin (PowerPozz^TM), stirring, until range estimation solution becomes uniformly, to prepare geopolymer resin.? In individual container, make 0.240g cetyl trimethylammonium bromide ((C₁₆H₃₃)N(CH₃)₃Br, CTAB) it is dissolved in 140ml In ionized water.CTAB aqueous solution is poured into geopolymer resin, using mechanical agitator (STIR-PAK model 4554-10, Cole Parmer) stir about 30 minutes.Once stopping stirring, make gained particle precipitating, filtration drying, to obtain powder production Product.For the dispersibility in chloroform that the product is shown better than dispersibility in water, this shows the particle to a certain extent It is hydrophobic.

7.3g NaOH is dissolved in 9.5g water by embodiment 4., then thereto be added 122.2g sodium metasilicate (~ 10.6%Na₂O ,~26.5%SiO₂).The solution is stirred, until it becomes uniform with visual observations.In the solution, add Enter 61.0g metakaolin, stir, until range estimation solution becomes uniformly, to prepare geopolymer resin.In a separate container, Make 2.4g cetyl trimethylammonium bromide ((C₁₆H₃₃)N(CH₃)₃Br, CTAB) it is dissolved in 1400ml deionized water.It will 100ml CTAB aqueous solution pours into geopolymer resin, and stir about 1 minute.Then using homogenizer (IKA T25 number ULTRA-) homogenized the mixture about 10 minutes with 10000rpm.Then, remaining CTAB solution is poured into mixed It closes in object, which is stirred about 30 minutes using mechanical agitator (STIR-PAK model 4554-10, Cole Parmer). After stopping stirring, gained suspended substance is centrifuged, being washed with deionized is more than three times.Last with 2000rpm progress After centrifugation was less than 10 minutes, supernatant is toppled over, obtain the particle dispersion of the viscosity containing 62wt% water.

25.0g NaOH is dissolved in 71.5g water by embodiment 5..The solution is stirred, until it becomes with visual observations Uniformly.In the solution, 60.0g metakaolin, stirring is added, until range estimation solution becomes uniformly, to obtain geopolymer Resin.When solution is cooling in ice bath, it is gradually added into the dense H of 35.5g₃PO₄(85%).Stir the solution about 15 minutes, thus Obtain uniform mixture.Once stopping stirring, make gained particle precipitating, filtration drying obtains powder-product.The product is aobvious For the dispersibility in water shown better than the dispersibility in chloroform, it is hydrophilic that this, which shows the particle to a certain extent,.

6.85g NaOH is dissolved in 12.32g water by embodiment 6., then thereto be added 17.61g sodium metasilicate (~ 10.6%Na₂O ,~26.5%SiO₂).Laboratory blender (IKARW60 digital mixer) is used with 800rpm to stir this molten Liquid, until it becomes uniform with visual observations.6.17g metakaolin is added into the solutionWith 800rpm continues stirring 35 minutes, this generates the geopolymer resin that rough nominal Na:Al:Si atomic ratio is 3:1:2.It will The resin material is transferred in the polypropylene containers of sealing, in lab oven (Yamato DKN400) in 60 DEG C to its into Row heating, provides geopolymer resin material.For 24 hours, a small amount of material is taken out after 48h and 72h.The resin material sample It is soft, or even its deformation can be made with hand after the heating of 72h.When being mildly shaken to mixed lower placement in water, they Split into fine granular.Fig. 3 A and 3B show the x-ray diffractogram of powder of the sample taken out after for 24 hours with 72h respectively Sample, wherein most of peaks Bragg can be attributed to faujasite-type (FAU) structure.Then in a large amount of water in 90 DEG C heating by The particle dispersion for the sample resins material preparation taken out after 48h is for 24 hours.After heating, by centrifugation, subsequent incline Analysis and the drying in lab oven, to remove water from the particle of dispersion.Its x-ray diffractogram of powder sample is shown in figure In 3C.Fig. 3 D (showing for comparing) is the simulation pattern with the NaX zeolite of faujasite-type (FAU) structure.

6.85g NaOH is dissolved in 12.32ml water by embodiment 7., then thereto be added 17.61g sodium metasilicate (~ 10.6%Na₂O ,~26.5%SiO₂).Laboratory blender (IKA RW60 digital mixer) is used with 800rpm to stir this molten Liquid, until it becomes uniform with visual observations.6.17g metakaolin is added into the solutionWith 800rpm continues stirring 35 minutes, this generates the geopolymer resin that rough nominal Na:Al:Si atomic ratio is 3:1:2.It will The resin material is transferred in open propylene beaker, is heated in 60 DEG C to it in lab oven (Yamato DKN400) 7 days, geopolymer resin material is obtained, the geopolymer resin material is uniform and hard solid.It then will about 5g Resin material is placed in 100ml deionized water, is heated for 24 hours at 90 DEG C.Resin material part is observed during heating in water Split into particle.Water is removed from particle by decantation first.It is further lightly ground the particle, in lab oven It is dried in 110 DEG C overnight.Final products show Barret-Joyner-Halenda (BJH) cumulative volume (pore size It is 0.3cm for 2nm to 300nm)³/ g, the hole that average cell size is 17nm.Nitrogen Brunauer-Emmett-Teller (BET) Surface area is 115m²/g.The x-ray diffractogram of powder sample of product is shown in Fig. 4, the peak wherein most Bragg can be returned Belong to compose sodalite type (SOD) structure of (stick spectrum) display by line chart.

6.8g NaOH is dissolved in 12.3ml water and 17.6g sodium silicate solution (59%H by embodiment 8.₂O, 27%SiO₂With In mixture 14%NaOH).In the solution, 8.6g metakaolin is addedUsing laboratory blender (IKARW60 digital mixer) with 800rpm stirring 40 minutes, it was 3:1:2 that this, which generates rough nominal Na:Al:Si atomic ratio, Geopolymer resin.The liquid is transferred in the polypropylene containers of sealing, at lab oven (Yamato DKN400) In the geopolymer resin material for obtaining paste for 24 hours is heated to it in 60 DEG C.By resin material in being placed at room temperature for big It measures in deionized water, is lightly ground, to obtain particle in water.Particle is washed repeatedly, so that the pH of particle dispersion is down to About 7.By being centrifuged 10 minutes in 6000rpm and being dried overnight at 85 DEG C, to collect gained particle.These particles are shown Nitrogen Brunauer-Emmett-Teller (BET) surface area be 497m²/ g, wherein 279m²/ g comes from micropore.These particles Barret-Joyner-Halenda (BJH) De contamination accumulation pore volume be 0.82cm³/ g, micro pore volume are 0.13 cm³/g。 Observe that Barret-Joyner-Halenda (BJH) De contamination hole width is 12nm.Fig. 5 A, 5B and 5C respectively illustrate the production Nitrogen adsorption isotherm, pore size distribution and the scanning electron microscope image of product.Fig. 5 D is the X-ray diffraction pattern of product, Show that the peak Bragg, the peak Bragg can be attributed to compose the faujasite of display by line chart in its X-ray pattern Type (FAU) structure.

4.19g NaOH is dissolved in 8.64ml water by embodiment 9., then thereto be added 1.85g sodium metasilicate (~ 10.6%Na₂O ,~26.5%SiO₂).Laboratory blender (IKA RW60 digital mixer) is used with 800rpm to stir this molten Liquid, until it becomes uniform with visual observations.6.17g metakaolin is added into the solutionWith 800rpm continues stirring 35 minutes, this generates the geopolymer resin that rough nominal Na:Al:Si atomic ratio is 2:1:1.15. 9.7ml canola oil is added into the mixture, stirring 10 minutes is continued with 800rpm, this generates the uniform geopolymer of viscosity Resin material.The liquid is poured into the polypropylene containers of sealing, in 60 DEG C in lab oven (Yamato DKN400) Heating 2 days, to obtain the geopolymer resin material of solid, the geopolymer resin material is soft, and is easy to use Record book in accordion form is broken.Then about 5g solid is placed in 100ml deionized water, is heated for 24 hours at 90 DEG C, solid is split into during this period Particle in water.By decantation, then replaced with fresh deionized water, and 90 DEG C heating for 24 hours, be repeated twice, from Water is removed in grain.It is then poured off water from particle, is rinsed particle 2 minutes with deionized water, in 110 in lab oven It DEG C is dried overnight.Final products show Barret-Joyner-Halenda (BJH) cumulative volume (pore size be 2nm extremely It 300nm) is 0.15cm³/ g, the hole that average cell size is 8nm.Micro pore volume is 0.10cm³/g.Nitrogen Brunauer- Emmett-Teller (BET) surface area is 283m²/ g, wherein 207m²/ g comes from micropore.The powder X-ray of product is shown in Fig. 6 X ray diffraction pattern, the peak wherein most Bragg can be attributed to compose faujasite-type (FAU) structure of display by line chart.

3.99g NaOH is dissolved in 8.11ml water by embodiment 10., then thereto be added 3.09g sodium metasilicate (~ 10.6%Na₂O ,~26.5%SiO₂).Laboratory blender (IKARW60 number mixed, clutch) is used with 800rpm to stir this molten Liquid, until it becomes uniform with visual observations.6.17g metakaolin is added into the solutionWith 800rpm continues stirring 35 minutes, this generates the geopolymer resin that rough nominal Na:Al:Si atomic ratio is 2:1:1.25. 9.7ml canola oil is added into the mixture, stirring 10 minutes is continued with 800rpm, this generates the uniform geopolymer of viscosity Resin material.The liquid is poured into the polypropylene containers of sealing, in 60 DEG C in lab oven (Yamato DKN400) Heating 2 days, to obtain the geopolymer resin material of solid, the geopolymer resin material is soft, and is easy to use Record book in accordion form is broken.Then about 5g solid is placed in 100ml deionized water, is heated for 24 hours at 90 DEG C, solid is split into during this period Particle in water.By decantation, then replaced with fresh deionized water, and 90 DEG C heating for 24 hours, be repeated twice, from Water is removed in grain.Water is then poured off from particle, finally with deionized water rinse particle 2 minutes, in lab oven in 110 DEG C are dried overnight.Final products show Barret-Joyner-Halenda (BJH) cumulative volume (pore size be 2nm extremely It 300nm) is 0.17cm³/ g, the hole that average cell size is 7nm.Micro pore volume is 0.07cm³/g.Nitrogen Brunauer- Emmett-Teller (BET) surface area is 254m²/ g, wherein 144m²/ g comes from micropore.The powder X-ray of product is shown in Fig. 7 X ray diffraction pattern, the peak wherein most Bragg can be attributed to compose faujasite-type (FAU) structure of display by line chart.

3.04g NaOH is dissolved in 3.35ml water by embodiment 11., then thereto be added 7.75g sodium metasilicate (~ 10.6%Na₂O ,~26.5%SiO₂).Laboratory blender (IKA RW60 digital mixer) is used with 800rpm to stir this molten Liquid, until it becomes uniform with visual observations.3.80g metakaolin is added into the solutionWith 800rpm continues stirring 35 minutes, this generates the geopolymer resin that rough nominal Na:Al:Si atomic ratio is 3:1:2.To 8.0ml canola oil is added in the mixture, stirring 10 minutes is continued with 800rpm, this generates the uniform geopolymer tree of viscosity Rouge material.The liquid is poured into the polypropylene containers of sealing, is added in lab oven (Yamato DKN400) in 60 DEG C Heat 2 days, to obtain the geopolymer resin material of solid, the geopolymer resin material is soft, and is easy to use hand It rolls over broken.Then about 5g solid is placed in 100ml deionized water, is heated for 24 hours at 90 DEG C, solid is split into during this period Particle in water.It by decantation, is then replaced with fresh deionized water, and is heated for 24 hours at 90 DEG C, is repeated twice, from particle Middle removing water.Water is then poured off from particle, finally with deionized water rinse particle 2 minutes, in lab oven in 110 DEG C are dried overnight.Final products show Barret-Joyner-Halenda (BJH) cumulative volume (pore size 2nm It is 0.54cm to 300nm)³/ g, the hole that average cell size is 11nm.Micro pore volume is 0.13cm³/g.It is shown in Fig. 8 A Barret-Joyner-Halenda (BJH) pore size distribution.Nitrogen Brunauer-Emmett-Teller (BET) surface area is 467m²/ g, wherein 289m²/ g comes from micropore.Nitrogen adsorption isotherm is shown in Fig. 8 B.The powder of product is shown in Fig. 8 C X-ray diffraction pattern, the peak wherein most Bragg can be attributed to compose faujasite-type (FAU) knot of display by line chart Structure.Fig. 8 D and 8E respectively illustrate the scanning electron micrographs (SEM) and transmission electron micrograph (TEM) of product.

4.93g NaOH is dissolved in 5.42ml water by embodiment 12., then thereto be added 12.56g sodium metasilicate (~ 10.6%Na₂O ,~26.5%SiO₂).Laboratory blender (IKA RW60 digital mixer) is used with 800rpm to stir this molten Liquid, until it becomes uniform with visual observations.6.15g metakaolin is added into the solutionWith 800rpm continues stirring 35 minutes, this generates the geopolymer resin that rough nominal Na:Al:Si atomic ratio is 3:1:2.To 12.96ml abandoned vegetable oil is added in the mixture, stirring 10 minutes is continued with 800rpm, this generates equably gathering for viscosity Polymer resin material.The liquid is poured into the polypropylene containers of sealing, in lab oven (Yamato DKN400) in 60 DEG C are heated 2 days, to obtain the geopolymer resin material of solid, the geopolymer resin material is soft, and easily In broken with record book in accordion form.Then about 5g solid is placed in 100ml deionized water, is heated at 90 DEG C for 24 hours, during this period solid point It is cleaved into particle in water.It by decantation, is then replaced with fresh deionized water, and is heated for 24 hours at 90 DEG C, is repeated twice, To remove water from particle.It is then poured off water from particle, is rinsed particle 2 minutes with deionized water, in lab oven It is dried overnight in 110 DEG C.Final products show Barret-Joyner-Halenda (BJH) cumulative volume (pore size 2nm It is 0.33cm to 300nm)³/ g, the hole that average cell size is 12nm.Micro pore volume is 0.18cm³/g.Nitrogen Brunauer- Emmett-Teller (BET) surface area is 549m²/ g, wherein 392m²/ g comes from micropore.The powder X-ray that product is shown in Fig. 9 is penetrated Ray diffraction diagram sample, the peak wherein most Bragg can be attributed to compose faujasite-type (FAU) structure of display by line chart.

5.28g NaOH is dissolved in 8.1g deionized water by embodiment 13., and 8.82g sodium metasilicate is then added thereto (~10.6%Na₂O ,~26.5%SiO₂).Using laboratory blender, (Stir-Pak laboratory blender, 4554-10 are obtained The solution is stirred from Cole-Parmer Instrument Company), until it becomes uniform with visual observations.At this In solution, 4.40g metakaolin, stirring is added, until range estimation solution becomes uniformly, to prepare geopolymer resin.Independent Container in, make 12.49g iron chloride (FeCl₃·6H₂O it) is dissolved in 10ml methanol.By FeCl₃·6H₂O solution adds dropwise Enter into geopolymer resin, while agitating resin.By the small increase of resin material volume it can be inferred that, during churning Most methanol evaporates.14ml canola oil is added to resulting reddish tan mushily in polymer resin material, is stirred The material is mixed about 10 minutes, in lab oven (Yamato DKN400) for 24 hours in 60 DEG C of heating, to obtain reddish tan Another geopolymer resin material.Carbon thermal reduction for iron, by this above-mentioned reddish tan solid abrasive of 2.0g at essence Fine powder heats it in 600 DEG C under argon gas stream in tube furnace (Thermo Scientific TF55030A-1) 3h, to obtain 1.29g black powder.The black powder shows about 28m²The nitrogen adsorption Brunauer-Emmett- of/g Teller (BET) surface area.A part of black powder is immersed in diluted hydrochloric acid, it is more than 4h which, which generates bubble,.

2.5g NaOH is dissolved in 3.6g water by embodiment 14..The solution is stirred, until it becomes equal with visual observations Even.In the solution, 6.0g metakaolin, stirring is added, until range estimation solution becomes uniformly, to obtain geopolymer resin. When resin is cooling in ice bath, it is gradually added into the dense H of 3.6g₃PO₄(85%), stir about 5 minutes obtain uniform mixture. The pH of the mixture is about 7.Under different conditions to three different samples of the homogeneous mixture prepared under the same conditions It is dried.In the sample of drying at room temperature, (water loss rate is lower than 5%) is all no solid even after 18h in draught cupboard Change.After 18h, it is cured in 60 DEG C and 85 DEG C of dry samples (respective water loss rate is 38% and 48%).Figure 10 Show the x-ray diffractogram of powder sample in 85 DEG C of dry products.

5.0g NaOH is dissolved in 7.2g water by embodiment 15..The solution is stirred, until it becomes equal with visual observations Even.In the solution, 12.0g metakaolin, stirring is added, until range estimation solution becomes uniformly, to obtain geopolymer tree Rouge.When resin is cooling in ice bath, it is gradually added into the dense H of 4ml₂SO₄The solution of (95% -98%) and 16ml water, stir about 5 divide Clock obtains uniform mixture.The pH of the mixture is about 7.By sample in room temperature, 60 DEG C or 85 DEG C of dryings, it is made to become solid Change.

5.0g NaOH is dissolved in 7.2g water by embodiment 16..The solution is stirred, until it becomes equal with visual observations Even.In the solution, 12.0g metakaolin, stirring is added, until range estimation solution becomes uniformly, to obtain geopolymer tree Rouge.When resin is cooling in ice bath, it is gradually added into 3.5g glacial acetic acid, stir about 5 minutes, obtains uniform mixture.This is mixed The pH for closing object is about 7.By sample in 60 DEG C of dryings, which becomes to solidify.

Embodiment 17. is by 0.160g TiO₂Nano particle (anatase) is dispersed in the dense H of 8.245g₃PO₄(85%) in.? In individual container, 5.0g NaOH is dissolved in 14.4g water.The solution is stirred, until it becomes uniform with visual observations 's.In the solution, 12.0g metakaolin, stirring is added, until range estimation solution becomes uniformly, to obtain geopolymer resin. TiO is gradually added into resin₂Dispersion is stirred simultaneously, obtains geopolymer resin material.Resin material is divided into Three parts, (room temperature, 60 DEG C and 85 DEG C) are dried and cured each section at different conditions.Figure 11 is shown at 85 DEG C The x-ray diffractogram of powder sample of dry product.

2.0g acetylene carbon black is homogeneously mixed in 12.5g glycerol by embodiment 18..In a separate container, will 0.73g NaOH is dissolved in 0.95g water, and 12.22g sodium metasilicate (~10.6%Na is then added thereto₂O ,~26.5% SiO₂).The solution is stirred, until it becomes uniform with visual observations.6.10g metakaolin is added into solution, stirs, Until range estimation solution becomes uniformly, to obtain geopolymer resin.Futher stir about 20 points of resulting geopolymer resin Clock.The mixture of carbon black and glycerol is added in geopolymer resin with the weight ratio of 3:1, stirs the mixture, until they Become uniformly, to obtain carbon black/glycerol-geopolymer resin material.By using doctor blade method, by a part of resin Material is applied on microscopic slide.Subsequent to pyrolysis glycerol, in argon gas in tube furnace (Thermo Scientific) It flows down and heats glass slide 10h in 500 DEG C.Final black film on glass slide is shown about on volt-ohmmeter The resistance of 700 Ω.

2.5g NaOH is dissolved in 3.6g water by embodiment 19..The solution is stirred, until it becomes equal with visual observations Even.In the solution, 6.0g metakaolin, stirring is added, until range estimation solution becomes uniformly, to obtain geopolymer resin. When resin is cooling in ice bath, it is gradually added into the dense H of 3.6g₃PO₄(85%), stir about 5 minutes obtain uniform mixture. 2ml phosphate buffer (pH=7) is added in mixture, is stirred simultaneously.Final homogeneous mixture is divided into three Part is at different conditions dried three samples.For the sample in draught cupboard in drying at room temperature, mixture Solidification has carried out about 1 hour.Become solid after 3h in 60 DEG C and 85 DEG C of dry samples in closed lab oven Change.

5.0g NaOH is dissolved in 14.3g water by embodiment 20..The solution is stirred, until it becomes with visual observations Uniformly.In the solution, 12.0g metakaolin, stirring is added, until range estimation solution becomes uniformly, to obtain geopolymer tree Rouge.When resin is cooling in ice bath, it is gradually added into the dense H of 7.1g₃PO₄(85%), stir about 5 minutes, are uniformly mixed Object.In a separate container, make 0.482g cetyl trimethylammonium bromide ((C₁₆H₃₃)N(CH₃)₃Br, CTAB) it is dissolved in In 200ml deionized water.CTAB aqueous solution is poured into uniform mixture, stir about 1 minute.Then homogenizer is used (IKAT25 number ULTRA-) homogenized about 10 minutes with 10000rpm to mixture solution.Once stopping It only stirs, makes gained particle precipitating, filtration drying, to obtain powder-product.The dispersion in chloroform that the product is shown Property better than dispersibility in water, it is hydrophobic that this, which shows the particle to a certain extent,.CHN is analysis shows the material contains 2.46wt% carbon and 0.14wt% nitrogen.Product shows about 22m²The nitrogen adsorption Brunauer-Emmett-Teller of/g (BET) surface area.Figure 12 A and 12B respectively illustrate the transmission electron microscope (TEM) and scanning electron microscope of product (SEM) image.According to ICP as a result, the Na:Al:P ratio of product is 1.0:11.7:1.0.Since silicate is in used sample Dissolubility is poor under product analysis condition, so not estimating the amount of Si.

25.0g NaOH is dissolved in 71.5g water by embodiment 21..The solution is stirred, until it becomes with visual observations Uniformly.In the solution, 60.0g metakaolin, stirring is added, until range estimation solution becomes uniformly, to obtain geopolymer tree Rouge.When resin is cooling in ice bath, it is gradually added into the dense H of 35.5g₃PO₄(85%), stir about 15 minutes, are uniformly mixed Close object.In a separate container, make 2.410g cetyl trimethylammonium bromide ((C₁₆H₃₃)N(CH₃)₃Br, CTAB) it is dissolved in In 1000ml deionized water.The CTAB aqueous solution of 100ml is poured into uniform mixture, stir about 1 minute.Then it uses Homogenizer (IKA T25 number ULTRA-) homogenized about 10 points with 10000rpm to mixture solution Clock.After homogenizing, remaining CTAB solution is poured into mixture solution, using mechanical agitator (STIR-PAK model 4554-10, Cole Parmer) stir about 30 minutes.After discontinuation of the stirring, suspended substance is centrifuged, using deionized water Carrying out washing is more than three times.After being finally centrifuged with 2000rpm less than 10 minutes, topples over supernatant, obtain containing 60wt% The particle dispersion of the viscosity of water.

0.73g NaOH is dissolved in 0.95g water by embodiment 22., then thereto be added 12.22g sodium metasilicate (~ 10.6%Na₂O ,~26.5%SiO₂).The solution is stirred, until it becomes uniform with visual observations.In the solution, it is added 6.10g metakaolin, stirring, until range estimation solution becomes uniformly, to obtain geopolymer resin.Futher stir resin about 20 minutes.5ml resin is transferred in centrifuge tube, 5ml ethyl alcohol is added thereto.The pipe then is sealed with lid, is acutely shaken to mixed. After standing about 1 minute, which is divided into two layers, in the geopolymer resin material of lower layer and in the supernatant on upper layer Ethyl alcohol.Supernatant is removed from resin material by decantation.Repeat alcohol treatment four times of this resin.Add at 110 DEG C The resulting tackifying resin material 18h of heat, obtains geopolymer.CHN is analysis shows the material contains 0.21wt% carbon.Figure 13 thermogravimetric analysis (TGA) curves (solid line) for comparing geopolymer are prepared but with by identical nominal composition without second Thermogravimetric analysis (TGA) curve (dotted line) of the geopolymer of alcohol processing.The result shows that as dehydration and caused by weight loss, The former material contains less water than the latter.

0.73g NaOH is dissolved in 0.95g water by embodiment 23., then thereto be added 12.22g sodium metasilicate (~ 10.6%Na₂O ,~26.5%SiO₂).The solution is stirred, until it becomes uniform with visual observations.It is added into solution 6.10g metakaolin, stirring, until range estimation solution becomes uniformly, to obtain geopolymer resin.It polymerize with futher stirring Resin about 20 minutes.The total volume of resin is 11ml.5.0ml glycerol is added in 5.0ml geopolymer resin, stirring should Mixture about 10 minutes, obtain uniform geopolymer resin material.5.0ml resin material is transferred in centrifuge tube, Xiang Qi Middle addition 5.0ml ethyl alcohol.The pipe then is sealed with lid, is acutely shaken to mixed.After standing about 1 minute, which is divided into two Layer, the geopolymer resin material in lower layer and the supernatant ethyl alcohol on upper layer.Supernatant is removed from resin material by decantation Liquid ethyl alcohol.The supernatant of about 25wt% is glycerol, this shows that the alcohol treatment of geopolymer resin material is mentioned from resin material A certain amount of glycerol is taken.Alcohol treatment four times of this geopolymer resin material are repeated, until supernatant is without any The glycerol of significant quantity.In 110 DEG C of resulting tackifying resin material 18h of heating, geopolymer is obtained.CHN was analysis shows should Material contains the carbon of 11.9wt%.Figure 14 A shows the TGA curve of material, until about 400 DEG C do not show significant weight Amount loss, reduces about 18% in 400 DEG C of weight suddenly.In fig. 14b, by the FT-IR map (bottom) of geopolymer with It is not compared using the FT-IR map (top) of the geopolymer of glycerol preparation.The former shows 2900cm^-1(CH stretching) Neighbouring and 1450cm^-1(CH₂Bending) neighbouring strong absworption peak, this demonstrate the presence of the glycerol moiety in product material, and The latter does not have.

Embodiment 24. keeps making 6.04g NaOH be dissolved in 10.85ml in underwater sealing PA tube in ice bath In water.Then by 15.51g sodium metasilicate (~10.6%Na₂O ,~26.5%SiO₂) be added in the above solution, it is mixed using laboratory Clutch is stirred under water in a water bath with 800rpm, until becoming uniform with visual observations solution.It is added into solution 7.6g metakaolinContinue stirring 40 minutes with 800rpm, this generates rough nominal Na:Al:Si atom Than the geopolymer resin for 3:1:2.The geopolymer resin is poured into PA tube, its is gas-tight seal, in laboratory It is heated one day in baking oven in 60 DEG C, obtains the mushily polymer resin material that pH value is about 14.By the paste of about half from It takes out in container, is rinsed with a large amount of water, the paste is made to be subjected to centrifugation 10 minutes in 5000rpm.Topple over resulting supernatant (pH It is about 14), to obtain fine powdered solid.Fine powdered solid is rinsed using more fresh water, makes it in 5000rpm It is subjected to centrifugation 10 minutes, resulting supernatant is toppled over, to obtain fine powdered solid.It repeats to rinse, be centrifuged and be decanted step Suddenly, until supernatant reaches close to neutral pH.It is in 110 DEG C that neutral fine powdered solid is dry in lab oven Overnight.Final product shows that (pore size is 2nm to 300nm) to Barret-Joyner-Halenda (BJH) cumulative volume For 0.71cm³The mesoporous and t- figure micro pore volume of/g is 0.13cm³The micropore of/g.BJH De contamination average pore width is 12nm, BJH De contamination pore size distribution is shown in Figure 15.Nitrogen Brunauer-Emmett-Teller (BET) surface area is 497m²/ G, nitrogen adsorption isotherm are shown in Figure 16.

Remaining mushily polymer resin material 18 day in total is further heated at 60 DEG C.It then uses largely in water 0.1M HCl rinse the paste, make its 5000rpm be subjected to centrifugation 10 minutes, topple over obtained supernatant (pH=13), from And obtain fine powdered solid.Fine powdered solid is rinsed using more 0.1M HCl in water, make its 5000rpm is subjected to centrifugation 10 minutes.Topple over resulting supernatant, obtains fine powdered solid.Repeat rinse, centrifugation and on The decantation steps of clear liquid, until supernatant reaches neutral pH.It will be neutral fine powdered in 110 DEG C in lab oven Solid is dried overnight.Final product shows Barret-Joyner-Halenda (BJH) cumulative volume (pore size 2nm It is 0.85cm to 300nm)³The mesoporous and t- figure micro pore volume of/g is 0.22cm³The micropore of/g.The BJH De contamination hole that is averaged is wide Degree is 16nm, and BJH De contamination pore size distribution is shown in Figure 17.Nitrogen Brunauer-Emmett-Teller (BET) surface area For 688m²/ g, nitrogen adsorption isotherm are shown in Figure 18.

Embodiment 25. keeps making 6.85g NaOH be dissolved in 12.32ml in underwater sealing PA tube in a water bath In water.Then by 17.61g sodium metasilicate (~10.6%Na₂O ,~26.5%SiO₂) be added in the above solution, it is mixed using laboratory Clutch is stirred under water in a water bath with 800rpm, until becoming uniform with visual observations solution.It is added into solution 8.62g metakaolinContinue stirring 40 minutes with 800rpm, it is former that this generates rough nominal Na:Al:Si Son geopolymer resin more uniform than range estimation for 3:1:2.Into mixture, addition~23ml canola oil, obtains substantially 1:1 Oil: water volume ratio continues stirring 10 minutes with 800rpm, this generates viscosity, uniform geopolymer resin material.It will The resin material pours into 250ml polypropylene opening beaker.Then in 60 DEG C of heating polypropylene beakers 5 in lab oven It, to obtain uniform and hard geopolymer resin material.Then by solid resin material folding be broken into about 2cm × 2cm × The block of 2cm, and place it in 500ml deionized water, for 24 hours in 90 DEG C of heating.Solid is observed during heating in water Block splitting is at fine powder.Then it is poured off water from particle, particle is washed with deionized 2 minutes.In lab oven Particle drying is stayed overnight in 110 DEG C.The scanning electron micrographs (SEM) of product is shown in Figure 19.Final production is shown (pore size is that 2nm to 300nm) is 0.29cm to Barret-Joyner-Halenda (BJH) cumulative volume³/ g mesoporous and T- figure micro pore volume is 0.18cm³The micropore of/g.BJH De contamination average pore width is 16nm, BJH De contamination pore size distribution It is shown in Figure 20.Nitrogen Brunauer-Emmett-Teller (BET) surface area is 511m²/ g, nitrogen adsorption isotherm are shown in In Figure 21.Figure 22 shows the x-ray diffractogram of powder sample of sample, and the simulated diffraction pattern of zeolite NaX (FAU) passes through line Map is shown.

248.87g NaOH is dissolved in 258.89ml water by embodiment 26., and 1172.75g silicic acid is then added thereto Sodium (~10.6%Na₂O ,~26.5%SiO₂).Laboratory blender is used to stir the solution with 400rpm, until being seen with range estimation It examines it and becomes uniform.586.16g metakaolin is added into solutionContinue 35 points of stirring with 800rpm Clock, this generates the geopolymer resin that rough nominal Na:Al:Si atomic ratio is 2:1:2.950ml mustard is added into mixture Caul-fat obtains the substantially oil of 1:1: water volume ratio, continues stirring 10 minutes with 800rpm, this generates geopolymer resinous wood Material.The resin material is poured into the sheet die having a size of from about 10 inches × 14 inches × 0.5cm.Sheet die is shifted Into the polypropylene containers of sealing, heated 2 days in lab oven in 60 DEG C.After 2 days, resin material is formed to be Geopolymer folding is broken into about 2.5cm × 2.5cm × 0.5cm block, and is divided into three by geopolymer Batch.Each batch is placed in the deionized water of about 3L, and is heated for 24 hours at 90 DEG C.During heating in water, gather with observing It closes object material part and splits into about 1cm × 1cm × 0.5cm particle.Water is removed from particle by decantation, then using new Fresh deionized water replacement, and heated for 24 hours at 90 DEG C.It is poured off water, is replaced again using fresh deionized water, is reheated 24h.It is then poured off water from particle, particle is washed with deionized 2 minutes.In 110 DEG C by particle in lab oven It is dried overnight.Final products show Barret-Joyner-Halenda (BJH) cumulative volume (pore size be 2nm extremely It 300nm) is 0.28cm³/ g, the hole that average cell size is 24nm.Nitrogen Brunauer-Emmett-Teller (BET) surface area For 160m²/g。

289.03g NaOH is dissolved in 317.78ml water by embodiment 27., and 736.60g silicic acid is then added thereto Sodium (~10.6%Na₂O ,~26.5%SiO₂).Laboratory blender is used to stir the solution with 400rpm, until being seen with range estimation It examines it and becomes uniform.360.81g metakaolin is added into solutionContinue 40 points of stirring with 800rpm Clock, this generates the geopolymer resin that rough nominal Na:Al:Si atomic ratio is 3:1:2.760.0ml is added into mixture Canola oil obtains the substantially oil of 1:1: water volume ratio, continues stirring 10 minutes with 800rpm, this generates geopolymer resin Material.The resin material is poured into the sheet die having a size of from about 10 inches × 14 inches × 0.5cm.Sheet die is turned It moves on in the polypropylene containers of sealing, is heated 4 days in lab oven in 60 DEG C, to obtain uniform, semi-rigid whole Body material solid.Then make in open air solids-conditioned 3 days, to obtain geopolymer.By geopolymer Folding is broken into about 2.5cm × 2.5cm × 0.5cm block, and is divided into three individual batches.It is placed on about 3L's for each batch In deionized water, and heated for 24 hours at 90 DEG C.During heating in water, observe that geopolymer part splits into size It is about 2cm × 2cm × 0.25cm to about 0.3cm × 0.3cm × 0.3cm smaller particle.It is removed from particle by being decanted Then water is replaced using fresh deionized water, and heat for 24 hours at 90 DEG C.It is poured off water, again using fresh deionized water Secondary replacement reheats for 24 hours.It is then poured off water from particle, particle is washed with deionized 2 minutes.In lab oven Particle drying is stayed overnight in 110 DEG C.Final products show Barret-Joyner-Halenda (BJH) cumulative volume (hole ruler Very little be 2nm to 300nm) is 0.54cm³/ g, the hole that average cell size is 11nm.Micro pore volume is 0.13cm³/g.Nitrogen Brunauer-Emmett-Teller (BET) surface area is 467m²/ g, wherein 289m²/ g comes from micropore.Figure 23 shows sample X-ray diffractogram of powder sample, wherein the simulated diffraction pattern of zeolite NaX (FAU) pass through line chart spectrum display.

2.62g NaOH is dissolved in 6.15ml water by embodiment 28., then thereto be added 12.34g sodium metasilicate (~ 10.6%Na₂O ,~26.5%SiO₂).Use laboratory blender to stir the solution with 400rpm, until with visual observations it Become uniform.6.17g metakaolin (Alfa Aesar) is added into solution, stirring 40 minutes is continued with 800rpm, this production The geopolymer resin that raw rough nominal Na:Al:Si atomic ratio is 2:1:2.13.4ml canola oil is added into mixture, The substantially oil of 1:1: water volume ratio is obtained, stirring 10 minutes is continued with 800rpm, this generates geopolymer resin material.It will The resin material pours into circular die.The mold is transferred in the polypropylene containers of sealing, in 60 in lab oven DEG C heating 2 days, to obtain disc-shaped whole geopolymer, a diameter of about 7.6cm, with a thickness of about 1cm.Then Geopolymer folding is broken into about 1cm × 1cm × 1cm block, and is placed it in 100ml deionized water, at 90 DEG C Heating is for 24 hours.During heating in water, it is smaller to observe that geopolymer part splits into about 1cm × 1cm × 0.25cm Particle.Water is removed from particle by decantation, is then replaced using fresh deionized water, and is heated for 24 hours at 90 DEG C.Topple over Fall water, replaced again using fresh deionized water, is reheated for 24 hours.It is then poured off water from particle, is washed with deionized water Wash particle 2 minutes.Particle drying is stayed overnight in 110 DEG C in lab oven.

2.62g NaOH is dissolved in 6.15ml water by embodiment 29., then thereto be added 12.34g sodium metasilicate (~ 10.6%Na₂O ,~26.5%SiO₂).Use laboratory blender to stir the solution with 400rpm, until with visual observations it Become uniform.6.17g metakaolin is added into solutionContinue stirring 40 minutes with 800rpm, this production The geopolymer resin that raw rough nominal Na:Al:Si atomic ratio is 2:1:2.13.4ml canola oil is added into mixture, The substantially oil of 1:1: water volume ratio is obtained, stirring 10 minutes is continued with 800rpm, this generates geopolymer resin material.It will The resin material pours into circular die.The mold is transferred in the polypropylene containers of sealing, in 60 in lab oven DEG C heating 2 days, to obtain disc-shaped whole geopolymer, a diameter of about 7.6cm, with a thickness of about 1cm.Then Geopolymer folding is broken into about 1cm × 1cm × 1cm block, and is placed it in 100ml deionized water, at 90 DEG C Heating is for 24 hours.During heating in water, observe that geopolymer part is split into having a size of from about 1cm × 1cm × 0.2cm extremely 0.5cm × 0.5cm × 0.05cm smaller particle.Water is removed from particle by decantation, then uses fresh deionized water Replacement, and heated for 24 hours at 90 DEG C.It is poured off water, is replaced again using fresh deionized water, is reheated for 24 hours.Then from It is poured off water in grain, particle is washed with deionized 2 minutes.Particle drying is stayed overnight in 110 DEG C in lab oven.

3.04g NaOH is dissolved in 4.44ml water by embodiment 30., then thereto be added 7.75g sodium metasilicate (~ 10.6%Na₂O ,~26.5%SiO₂).Use laboratory blender to stir the solution with 400rpm, until with visual observations it Become uniform.3.80g metakaolin is added into solutionContinue stirring 30 minutes with 800rpm, this production The geopolymer resin that raw rough nominal Na:Al:Si atomic ratio is 3:1:2.10.0ml canola oil is added into mixture, The substantially oil of 1:1: water volume ratio is obtained, stirring 10 minutes is continued with 800rpm, this generates geopolymer resin material.It will The resin material pours into circular die.The mold is transferred in the polypropylene containers of sealing, in 60 in lab oven DEG C heating 2 days, to obtain disc-shaped whole geopolymer, a diameter of about 7.6cm, with a thickness of about 0.5cm.So Geopolymer folding is broken into about 2cm × 2cm × 0.5cm block afterwards, and is placed it in 100ml deionized water, 90 DEG C of heating are for 24 hours.During heating in water, observe that geopolymer part is split into having a size of from about 0.2cm × 0.2cm × 0.05cm to 1cm × 1cm × 0.2cm smaller particle.Water is removed from particle by decantation, is then gone using fresh Ionized water replacement, and heated for 24 hours at 90 DEG C.It is poured off water, is replaced again using fresh deionized water, is reheated for 24 hours.With Water is poured off from particle afterwards, particle is washed with deionized 2 minutes.In 110 DEG C by particle drying mistake in lab oven Night.Final products show that (pore size is that 2nm to 300nm) is to Barret-Joyner-Halenda (BJH) cumulative volume 0.19cm³/ g, the hole that average cell size is 18nm.Micro pore volume is 0.05cm³/g.Nitrogen Brunauer-Emmett- Teller (BET) surface area is 159m²/ g, wherein 104.2m²/ g comes from micropore.

4.1g NaOH is dissolved in 6.55ml water by embodiment 31..Use laboratory blender should with 400 rpm stirring Solution, until it becomes uniform with visual observations.3.80g metakaolin is added into solutionWith 800rpm continues stirring 40 minutes, this generates the geopolymer resin that rough nominal Na:Al:Si atomic ratio is 3:1:1.To 6.6ml canola oil is added in mixture, obtains the substantially oil of 1:1: water volume ratio, stirring 10 minutes is continued with 800rpm, this Generate geopolymer resin material.The resin material is poured into circular die.The polypropylene that the mold is transferred to sealing is held In device, heated 2 days in lab oven in 60 DEG C, so that disc-shaped whole geopolymer is obtained, it is a diameter of About 7.6cm, with a thickness of about 0.5cm.Then make in open air geopolymer aging 1 day.Then the solid is rolled over It is broken into about 1cm × 1cm × 1cm block, and is placed it in 100ml deionized water, is heated for 24 hours at 90 DEG C.It heats in water Period observes that geopolymer part splits into smaller particle, and wherein most becomes fine powder, but there are one The big sheet-like particle of a little 1cm × 0.5cm × 0.05cm.Water is removed from particle by decantation, then using it is fresh go from Sub- water replacement, and heated for 24 hours at 90 DEG C.It is poured off water, is replaced again using fresh deionized water, is reheated for 24 hours.Then It is poured off water from particle, particle is washed with deionized 2 minutes.In 110 DEG C by particle drying mistake in lab oven Night.Final products show that (pore size is that 2nm to 300nm) is to Barret-Joyner-Halenda (BJH) cumulative volume 0.06cm³/ g, the hole that average cell size is 11nm.Nitrogen Brunauer-Emmett-Teller (BET) surface area is 16m²/g。

3.95g NaOH is dissolved in 8.12ml water by embodiment 32., then thereto be added 3.09g sodium metasilicate (~ 10.6%Na₂O ,~26.5%SiO₂).Use laboratory blender to stir the solution with 400rpm, until with visual observations it Become uniform.6.17g metakaolin is added into solutionContinue stirring 40 minutes with 800rpm, this production The geopolymer resin that raw rough nominal Na:Al:Si atomic ratio is 2:1:1.25.9.9ml mustard is added into mixture Oil obtains the substantially oil of 1:1: water volume ratio, continues stirring 10 minutes with 800rpm, this generates geopolymer resin material. The resin material is poured into cube mold.The mold is transferred in the polypropylene containers of sealing, in lab oven In heated 2 days in 60 DEG C, to obtain in the whole geopolymer of 3cm × 3cm × 3cm cubic shaped.It then should The cube folding of solid is broken into about 1cm × 1cm × 1cm block, and solidifies it 2 days in open air in 60 DEG C.Then Geopolymer block is placed in 100ml deionized water, and is heated for 24 hours at 90 DEG C.During heating in water, observe Geopolymer part splits into smaller having a size of from about 0.25cm × 0.25cm × 0.05cm to 1cm × 1cm × 0.25cm Particle.Water is removed from particle by decantation, is then replaced using fresh deionized water, and is heated for 24 hours at 90 DEG C.Topple over Fall water, replaced again using fresh deionized water, is reheated for 24 hours.It is then poured off water from particle, is washed with deionized water Wash particle 2 minutes.Particle drying is stayed overnight in 110 DEG C in lab oven.Final products show Barret-Joyner- (pore size is that 2nm to 300nm) is 0.17cm to Halenda (BJH) cumulative volume³/ g, the hole that average cell size is 7nm.Nitrogen Brunauer-Emmett-Teller (BET) surface area is 254m²/g。

3.60g NaOH is dissolved in 6.88ml water by embodiment 33., then thereto be added 6.17g sodium metasilicate (~ 10.6%Na₂O ,~26.5%SiO₂).Use laboratory blender to stir the solution with 400rpm, until with visual observations it Become uniform.6.17g metakaolin is added into solutionContinue stirring 40 minutes with 800rpm, this production The geopolymer resin that raw rough nominal Na:Al:Si atomic ratio is 2:1:1.5.10.5ml mustard is added into mixture Oil obtains the substantially oil of 1:1: water volume ratio, continues stirring 10 minutes with 800rpm, this generates geopolymer resin material. The resin material is poured into cube mold.The mold is transferred in the polypropylene containers of sealing, in lab oven In heated 2 days in 60 DEG C, to obtain in the whole geopolymer of 3cm × 3cm × 3cm cubic shaped.It then should The cube folding of solid is broken into about 1cm × 1cm × 1cm block, and solidifies it 2 days in open air in 60 DEG C.Then Geopolymer block is placed in 100ml deionized water, and is heated for 24 hours at 90 DEG C.During heating in water, observe Geopolymer part is split into having a size of from about 0.2cm × 0.2cm × 0.1cm to 1cm × 0.5cm × 0.2cm smaller Grain.Water is removed from particle by decantation, is then replaced using fresh deionized water, and is heated for 24 hours at 90 DEG C.It is poured off Water is replaced again using fresh deionized water, is reheated for 24 hours.It is then poured off water from particle, is washed with deionized Particle 2 minutes.Particle drying is stayed overnight in 110 DEG C in lab oven.Final products show Barret-Joyner- (pore size is that 2nm to 300nm) is 0.1cm to Halenda (BJH) cumulative volume³/ g, the hole that average cell size is 17nm.Nitrogen Brunauer-Emmett-Teller (BET) surface area is 18m²/g。

4.19g NaOH is dissolved in 8.64ml water by embodiment 34., then thereto be added 1.85g sodium metasilicate (~ 10.6%Na₂O ,~26.5%SiO₂).Use laboratory blender to stir the solution with 400rpm, until with visual observations it Become uniform.6.17g metakaolin is added into solutionContinue stirring 40 minutes with 800rpm, this production The geopolymer resin that raw rough nominal Na:Al:Si atomic ratio is 2:1:1.25.9.7ml mustard is added into mixture Oil obtains the substantially oil of 1:1: water volume ratio, continues stirring 10 minutes with 800rpm, this generates geopolymer resin material. The resin material is poured into circular die.The mold is transferred in the polypropylene containers of sealing, in lab oven It is heated 2 days in 60 DEG C, so that disc-shaped whole geopolymer is obtained, a diameter of about 7.6cm, with a thickness of about 0.5cm.Then geopolymer folding is broken into about a quarter, each piece is placed in 100ml deionized water, 90 DEG C heating for 24 hours.During heating in water, observe geopolymer part split into having a size of from about 0.1cm × 0.1cm × 0.05cm to 1.5cm × 1.5cm × 0.25cm smaller particle.Water is removed from particle by decantation, then using fresh Deionized water replacement, and heated for 24 hours at 90 DEG C.It is poured off water, is replaced again using fresh deionized water, is reheated for 24 hours. It is then poured off water from particle, particle is washed with deionized 2 minutes.Particle is done in 110 DEG C in lab oven It is dry overnight.Final products show that (pore size is 2nm to 300nm) to Barret-Joyner-Halenda (BJH) cumulative volume For 0.15cm³/ g, the hole that average cell size is 8nm.Nitrogen Brunauer-Emmett-Teller (BET) surface area is 283m²/ g。

17.3g KOH is dissolved in 30ml water by embodiment 35., and 6.2g vapor deposition titanium dioxide is then added thereto Silicon.Then the solution is stirred, until it becomes uniform with visual observations.In the solution, 11.4g metakaolin is added, uses Laboratory blender obtained estimating uniform geopolymer resin with 800rpm stirring 40 minutes.The viscosity of the resin is similar to The viscosity of honey.Then 30ml canola oil is added in geopolymer resin, is stirred for 10 minutes with 800rpm, thus To the uniform geopolymer resin material of range estimation.The resin material is poured into cube well (cubic wells) with 1 inch Silicone rubber mold in, and in 60 DEG C of heating 72h in lab oven, to obtain in the whole of cubic shaped Body geopolymer.By geopolymer leaching in the hot water (90 DEG C) for 24 hours, initial cube division during this period.So Afterwards in 120 DEG C of dry particles in a liquid in lab oven.These particles show about 133m²The nitrogen of/g Brunauer-Emmett-Teller (BET) surface area, about 0.62cm³The Barret-Joyner-Halenda (BJH) of/g is de- The BJH De contamination hole width of absorption accumulation pore volume and 18nm.

15.7g KOH is dissolved in 30ml water by embodiment 36., and 6.7g vapor deposition titanium dioxide is then added thereto Silicon.Then the solution is stirred, until it becomes uniform with visual observations.In the solution, 12.4g metakaolin is added, uses Laboratory blender obtained estimating uniform geopolymer resin with 800rpm stirring 40 minutes.The viscosity of the resin is similar to The viscosity of honey.Then 30ml canola oil is added in geopolymer resin, is stirred for 10 minutes with 800rpm, thus To geopolymer resin material.The resin material is poured into the silicone rubber mold with 1 inch of cube well, and In 60 DEG C of heating 72h in lab oven, to obtain the geopolymer in cubic shaped.By geopolymer material Material leaching in the hot water (90 DEG C) for 24 hours, initial cube division during this period.Then in 120 DEG C of dryings in lab oven Particle in a liquid.These particles show about 130m²Surface nitrogen Brunauer-Emmett-Teller (BET) of/g Product, about 0.83cm³The BJH De contamination of Barret-Joyner-Halenda (BJH) De contamination the accumulation pore volume and 25nm of/g Hole width.

17.3g KOH is dissolved in 30ml water by embodiment 37., and 6.2g vapor deposition titanium dioxide is then added thereto Silicon.Then the solution is stirred, until it becomes uniform with visual observations.In the solution, 11.4g metakaolin is addedUsing laboratory blender with 800rpm stirring 40 minutes, obtain estimating uniform geopolymer resin. The viscosity of the resin is similar to the viscosity of honey.Then 30ml canola oil is added in geopolymer resin, again with 800rpm Stirring 10 minutes, to obtain geopolymer resin material.The resin material is poured into the organic of cube well with 1 inch In silicon rubber mould, and in 60 DEG C of heating 72h in lab oven, to obtain the geopolymer in cubic shaped Material.By geopolymer leaching in the hot water (90 DEG C) for 24 hours, initial cube division during this period.Then in laboratory In 120 DEG C of dry particles in a liquid in baking oven.These particles show about 130m²The nitrogen Brunauer- of/g Emmett-Teller (BET) surface area, about 0.72cm³Barret-Joyner-Halenda (BJH) De contamination of/g accumulates hole The BJH De contamination hole width of volume and 22nm.

15.7g KOH is dissolved in 30ml water by embodiment 38., and 6.7g vapor deposition titanium dioxide is then added thereto Silicon.Then the solution is stirred, until it becomes uniform with visual observations.In the solution, 12.4g metakaolin is addedUsing laboratory blender with 800rpm stirring 40 minutes, obtain estimating uniform geopolymer resin. The viscosity of the resin is similar to the viscosity of honey.Then 30ml canola oil is added in geopolymer resin, again with 800rpm Stirring 10 minutes, to obtain geopolymer resin material.The resin material is poured into the organic of cube well with 1 inch In silicon rubber mould, and in 60 DEG C of heating 72h in lab oven, to obtain the geopolymer in cubic shaped Material.By geopolymer leaching in the hot water (90 DEG C) for 24 hours, initial cube division during this period.Then in laboratory In 120 DEG C of dry particles in a liquid in baking oven.These particles show about 124m²The nitrogen Brunauer- of/g Emmett-Teller (BET) surface area, about 0.76cm³Barret-Joyner-Halenda (BJH) De contamination of/g accumulates hole The BJH De contamination hole width of volume and 25nm.

11.5g KOH is dissolved in 13.7ml water to embodiment 39. and 19.3g derives from the KASIL-6 (12.58% of Pq Corp. K₂O；26.62%SiO₂；60.80% water) mixture in.Then the solution is stirred, until it becomes uniform with visual observations 's.In the solution, 10.0g metakaolin is added40 points are stirred using laboratory blender with 800rpm Clock obtains estimating uniform geopolymer resin.The viscosity of the resin is similar to the viscosity of honey.Then by 25ml canola oil It is added in geopolymer resin, is stirred for 10 minutes with 800rpm, to obtain geopolymer resin material.By the resin Material pours into the silicone mold with 1 inch of cube well, and in 60 DEG C of heating 72h in lab oven, to obtain Obtained the geopolymer in cubic shaped.Geopolymer leaching is for 24 hours, first during this period in the hot water (90 DEG C) The cube of beginning splits into little particle.Then in 120 DEG C of dry resulting particles in lab oven.The scanning electricity of product Sub- displaing micro picture (SEM) is shown in Figure 24.These particles show about 99m²The nitrogen Brunauer-Emmett-Teller of/g (BET) surface area, about 0.63cm³Barret-Joyner-Halenda (BJH) the De contamination accumulation pore volume and 26nm of/g BJH De contamination hole width.Figure 25 and Figure 26 respectively illustrates the BJH pore size distribution and nitrogen adsorption isotherm of product.

12.0g KOH is dissolved in 15.3ml water to embodiment 40. and 25.2g derives from the KASIL-6 (12.58% of Pq Corp. K₂O；26.62%SiO₂；60.80% water) mixture in.Then the solution is stirred, until it becomes uniform with visual observations 's.In the solution, 12.3g metakaolin is added40 points are stirred using laboratory blender with 800rpm Clock obtains estimating uniform geopolymer resin.The viscosity of the resin is similar to the viscosity of honey.Then by 30ml canola oil It is added in geopolymer resin, is stirred for 10 minutes with 800rpm, to obtain geopolymer resin material.By the resin Material pours into the silicone mold with 1 inch of cube well, and in 60 DEG C of heating 72h in lab oven, to obtain Obtained the geopolymer in cubic shaped.Soak geopolymer in water (23 DEG C) for 24 hours, during this period initially Cube split into fine sheet-like particle.It is then poured off water from particle, particle is washed with deionized 2 minutes.So Afterwards in 120 DEG C of dry resulting particles in lab oven.These particles show about 93m²The nitrogen Brunauer- of/g Emmett-Teller (BET) surface area, about 0.76cm³Barret-Joyner-Halenda (BJH) De contamination of/g accumulates hole (pore size is 2nm to 300nm) to the BJH De contamination average pore width of volume and 40nm.Figure 27 and Figure 28 respectively illustrate product BJH pore size distribution and nitrogen adsorption isotherm.

12.0g KOH is dissolved in 15.3ml water to embodiment 41. and 25.2g derives from the KASIL-6 (12.58% of Pq Corp. K₂O；26.62%SiO₂；60.80% water) mixture in.Then the solution is stirred, until it becomes uniform with visual observations 's.In the solution, 12.3g metakaolin is added40 points are stirred using laboratory blender with 800rpm Clock obtains estimating uniform geopolymer resin.The viscosity of the resin is similar to the viscosity of honey.Then by 30ml canola oil It is added in geopolymer resin, is stirred for 10 minutes with 800rpm, to obtain geopolymer resin material.By the resin Material pours into the silicone mold with 1 inch of cube well, and in 60 DEG C of heating 72h in lab oven, to obtain Obtained the geopolymer in cubic shaped.Geopolymer leaching is for 24 hours, first during this period in the hot water (90 DEG C) The cube of beginning splits into the particle with irregular shape.Then resulting dry in 120 DEG C in lab oven Grain.These particles show about 84m²Nitrogen Brunauer-Emmett-Teller (BET) surface area, the about 0.75cm of/g³/g Barret-Joyner-Halenda (BJH) De contamination accumulation pore volume and 31nm BJH De contamination average pore width (hole Having a size of 2nm to 300nm).Figure 29 and Figure 30 respectively illustrates the BJH pore size distribution and nitrogen adsorption isotherm of product.

Embodiment 42. keeps being dissolved in 11.26g NaOH in underwater sealing PA tube in a water bath 28.25ml in water.20.0g Cholla flying dust (Salt River Materials Group) is added into solution, with 800rpm stirs the mixture 40 minutes, this generates the geopolymer that rough nominal Na:Al:Si atomic ratio is 3:1:2.18 Resin.Geopolymer resin is poured into 50ml PA tube, airtight sealing is carried out to it, places it in baking oven later In, in 60 DEG C of heating sample 72h.Resulting geopolymer resin material is rinsed using 0.1M HCl largely in water, is made It is subjected to centrifugation 10 minutes in 5000rpm, topples over resulting supernatant (pH=13), obtains fine powdered solid.Using more More 0.1M HCl in water rinse fine powdered solid, it is made to be subjected to centrifugation 10 minutes in 5000rpm.Topple over gained Supernatant, obtain fine powdered solid.The decantation steps for repeating flushing, centrifugation and supernatant, in supernatant reaches Property pH.Neutral fine powdered solid is dried overnight in 110 DEG C in lab oven.

Embodiment 43. makes 11.26g NaOH be dissolved in 28.25ml in the sealing PA tube being maintained under water-bath In water.20.0g Cholla flying dust (Salt River Materials Group) is added into solution, it should with 800rpm stirring Mixture 40 minutes, this generated the geopolymer resin that rough nominal Na:Al:Si atomic ratio is 3:1:2.18.To mixture Middle addition~23ml canola oil obtains the substantially oil of 1:1: water volume ratio, continues stirring 10 minutes with 800rpm, this generation Geopolymer resin material.The resin material is poured into 50ml PA tube, airtight sealing is carried out to it, later by it It places in an oven, in 60 DEG C of heating sample 72h.Resulting resin material is placed in 500ml hot water in (90 DEG C), 90 DEG C of heating are for 24 hours.Then it is poured off water from particle, is washed particle 2 minutes using fresh hot water.In lab oven Particle drying is stayed overnight in 110 DEG C.

Although described above and appended claims disclose numerous embodiments, in following further implementation Other replaceable aspects of the invention are disclosed in mode.

A kind of method of embodiment 1. comprising:

Contact the first geopolymer resin material with liquid；With

At least part liquid is removed, material is obtained.

The method of 2. embodiment 1 of embodiment, wherein the first geopolymer resin material include silicate, aluminate, Aluminosilicate, organosilicate, organo-alumino-silicate, phosphate, silicophosphate, silicoaluminophosphate (silico ) or their combination aluminophosphates.

The method of 3. embodiment 1 or 2 of embodiment further includes one or more selected from following substance by merging Inorganic material and alkali or alkaline solution form the first geopolymer resin material: fumed silica, rice hull ash, Silicon ash, aluminate, aluminosilicate, organosilan, clay, mineral, metakaolin, calcined clay, activated clay, flies at silicate Ash, clinker, volcanic ash, burning multi-purpose waste material, glass powder and red mud.

The method of any one of 4. embodiment 1-3 of embodiment, wherein the first geopolymer resin material be it is acid or Alkaline solution comprising dissolution or partly soluble clay material, activated clay material or calcined clay material.

The method of any one of 5. embodiment 1-4 of embodiment, wherein the first geopolymer resin material includes that alkali is living The metakaolin or metakaolin of change or alkaline matter activation.

The method of any one of 6. embodiment 1-5 of embodiment, wherein the first geopolymer resin material includes aluminium silicon The aqueous slkali of hydrochlorate, water content are not more than 60wt% or 70wt%.

The method of any one of 7. embodiment 1-6 of embodiment, wherein the first geopolymer resin material includes atom The aqueous slkali of aluminosilicate than A:Al higher than 1, wherein A is any combination of alkali metal or alkali metal, and the aqueous slkali contains Water is not more than 60wt% or 70wt%.

The method of any one of 8. embodiment 1-7 of embodiment, wherein the first geopolymer resin material includes one kind Or the oxide or hydroxide or its hydrate of a variety of phosphorus, silicon, alkali metal, alkaline-earth metal.

The method of any one of 9. embodiment 1-8 of embodiment, wherein the first geopolymer resin material includes organic Silane, phosphoric acid, phosphate, hydrophosphate, hydrophosphate, organo-phosphine oxide, phosphate, silicophosphate, silicoaluminophosphate or Their combination.

The method of any one of 10. embodiment 1-9 of embodiment, wherein the first geopolymer resin material includes one Kind or a variety of other components, the component independently selected from molecule, monomer, oligomer, polymer, ion, salt, biomaterial, Structure directing agent, hole template, surfactant, cluster, nano particle, particle, fiber, filler or their combination.

The method of any one of 11. embodiment 1-9 of embodiment, wherein the first geopolymer resin material includes one Kind or a variety of other components, the component is independently selected from vegetable oil, vegetable oil, animal oil, abandoned vegetable oil, discarded animal Oil, fat, biodiesel, fatty acid, lipid, ester, carboxylic acid, the oil based on petroleum or their combination.

The method of any one of 12. embodiment 1-11 of embodiment, wherein it is not fully cured or partially cured and/or Aging the first geopolymer resin material.

The method of any one of 13. embodiment 1-12 of embodiment, wherein the first geopolymer resin material is in liquid Or semiliquid state, viscosity are higher than the viscosity of water.

The method of any one of 14. embodiment 1-13 of embodiment, wherein the first geopolymer resin material is soft Or semi-rigid.

The method of any one of 15. embodiment 1-14 of embodiment, wherein the first geopolymer resin material is solid Body.

The method of any one of 16. embodiment 1-15 of embodiment, wherein liquid and the first geopolymer resin material It is unmixing.

The method of any one of 17. embodiment 1-16 of embodiment, wherein liquid includes water.

The method of any one of 18. embodiment 1-17 of embodiment, wherein liquid includes organic solvent or organic molten The mixture of agent and water.

The method of any one of 19. embodiment 1-18 of embodiment, wherein liquid be acid solution, alkaline solution or PH buffer.

The method of any one of 20. embodiment 1-19 of embodiment, wherein liquid is the pH buffering for including biomaterial Agent.

The method of any one of 21. embodiment 1-20 of embodiment, wherein liquid includes solvent and dissolution, dispersion , cohesion, it is flocculated or suspend species, the species be selected from molecule, metal precursor, monomer, oligomer, polymer, Ion, salt, biomaterial, structure directing agent, hole template, surfactant, cluster, nano particle, particle, fiber, filler, Or their combination.

The method of 22. embodiment 13 of embodiment, wherein the viscosity of the organic solvent is higher than the viscosity of water.

The method of 23. embodiment 13 of embodiment, wherein the organic solvent is volatile.

The method of any one of 24. embodiment 1-23 of embodiment, wherein the first geopolymer resin material and liquid Contact generate particle dispersion or suspended substance.

The method of any one of 25. embodiment 1-24 of embodiment, wherein the first geopolymer resin material and liquid Contact generate mixture uniformly or non-uniformly.

The method of any one of 26. embodiment 1-25 of embodiment, wherein the first geopolymer resin material and liquid Contact change the first geopolymer resin material composition and/or pH.

The method of any one of 27. embodiment 1-26 of embodiment, wherein in controlled temperature, atmosphere, pressure, wet Degree level or combinations thereof carries out contact of the first geopolymer resin material with liquid.

The method of any one of 28. embodiment 1-27 of embodiment, wherein carrying out the first ground polymerization in high temperature or low temperature Contact of the resin material with liquid.

The method of any one of 29. embodiment 1-28 of embodiment, wherein by making liquid condense to the polymerization of the first ground Contact of the first geopolymer resin material with liquid is carried out on and/or within resin material.

The method of any one of 30. embodiment 1-29 of embodiment, wherein the first geopolymer resin material and liquid Contact include mix, be blended, being shaken to mixed, shearing, homogenizing, stirring, stirring, ultrasound or vibrate the first geopolymer resinous wood Material and liquid.

The method of any one of 31. embodiment 1-30 of embodiment, wherein the first geopolymer resin material and liquid Contact include crushing, pulverize, grind, grind, grind, be crushed, crush, smash to pieces, suppress or developing the first ground in a liquid Polymer resin material.

The method of any one of 32. embodiment 1-31 of embodiment, wherein the first geopolymer resin material and liquid Contact include by the leaching of the first geopolymer resin material in a liquid, or with liquid wash the first geopolymer resin material.

The method of any one of 33. embodiment 1-32 of embodiment, wherein the first geopolymer resin material and liquid Contact so that the first geopolymer resin material divides the particle to be formed in liquid.

The method of any one of 34. embodiment 1-33 of embodiment, wherein the first geopolymer resin material and liquid Contact change liquid composition.

The method of any one of 35. embodiment 1-34 of embodiment, wherein the first geopolymer resin material and liquid Contact one or more components in a liquid are transferred in the first geopolymer resin material.

The method of any one of 36. embodiment 1-35 of embodiment, wherein the first geopolymer resin material and liquid Contact one or more components of the first geopolymer resin material are transferred in liquid.

The method of any one of 37. embodiment 1-36 of embodiment, wherein the first geopolymer resin material includes Water, contact of the first geopolymer resin material with liquid is by least part water in the first geopolymer resin material It is transferred in liquid.

The method of any one of 38. embodiment 1-37 of embodiment, wherein the first geopolymer resin material and liquid Contact so that one or more components of liquid and the first geopolymer resin material one or more component reactions.

The method of any one of 39. embodiment 1-38 of embodiment, wherein the first geopolymer resin material and liquid Contact change the first geopolymer resin material viscosity.

The method of any one of 40. embodiment 1-39 of embodiment, wherein the first geopolymer resin material and liquid Contact change the ionic strength of liquid and/or the first geopolymer resin material.

The method of any one of 41. embodiment 1-40 of embodiment further includes being cured or partially cured the first ground to gather Polymer resin material, wherein the first geopolymer tree of contact acceleration or deceleration of the first geopolymer resin material with liquid The solidification of rouge material.

The method of any one of 42. embodiment 1-41 of embodiment, wherein the material includes a variety of particles.

The method of any one of 43. embodiment 1-42 of embodiment, wherein the material is powder.

The method of any one of 44. embodiment 1-43 of embodiment, wherein the material is point for including a variety of particles Granular media or suspended substance.

The method of any one of 45. embodiment 42-44 of embodiment, wherein the size of more than half particle less than 1 μm or Less than 1000 μm.

The method of any one of 46. embodiment 42-45 of embodiment, wherein the composition of particle is different from geopolymer The composition of resin material.

The method of any one of 47. embodiment 42-46 of embodiment, wherein liquid includes surfactant, by surface Activating agent is coupled on the surface of particle.

The method of any one of 48. embodiment 1-41 of embodiment, wherein the material is monolith.

The method of 49. embodiment 48 of embodiment, wherein the form of the monolith be block, plate, film, film, Coating, line, ball, pearl, pellet, bar or their combination.

The method of 50. embodiment 48 or 49 of embodiment, wherein the monolith includes biomaterial.

The method of any one of 51. embodiment 1-41 of embodiment, wherein the material is the second geopolymer resin Material.

The method of 52. embodiment 51 of embodiment, wherein the composition of the second geopolymer resin material and/or PH is different from the composition and/or pH of the first geopolymer resin material.

The method of 53. embodiment 51 or 52 of embodiment further includes the second geopolymer resin material of solidification, shape At solid.

The method of 54. embodiment 53 of embodiment, wherein solidification is included in environment temperature or when heated solidification or portion Divide solidification.

The method of 55. embodiment 53 or 54 of embodiment, wherein solidifying includes heating in controlled humidity.

The method of any one of 56. embodiment 53-55 of embodiment, wherein solidification includes stirring, being shaken to mixed, shearing, stirring Dynamic, ultrasound or oscillation.

The method of any one of 57. embodiment 53-56 of embodiment, wherein solidification includes spin coating (spinning), paving Exhibition (spreading) smoothes out (screeding), is spraying, distribution (dispending), injects, foams, shaping, molding, tearing up (ribboning), extrusion or pultrusion.

The method of any one of 58. embodiment 53-57 of embodiment, wherein the form of solid be monolith, plate, Film, film, coating, line, ball, pearl, pellet, bar or their combination.

The method of any one of 59. embodiment 53-58 of embodiment, wherein the solid is composite material comprising Organic material, polymer material, inorganic material, biomaterial or their combination.

The method of any one of 60. embodiment 1-59 of embodiment, wherein removing at least part liquid includes removing The liquid of more than half amounts.

The method of any one of 61. embodiment 1-60 of embodiment, wherein it includes heavy for removing at least part liquid It forms sediment, decantation, filter or be centrifuged.

The method of any one of 62. embodiment 1-61 of embodiment, wherein removing at least part liquid includes passing through Add flocculation, reunion, aggregation, cohesion or the coalescence of the particle that clarifying agent, flocculant or coagulant carry out.

The method of any one of 63. embodiment 1-62 of embodiment, wherein it includes dry for removing at least part liquid Dry, spray drying, freeze-drying, evaporation or dehydration.

The method of any one of 64. embodiment 1-63 of embodiment, wherein removing at least part liquid includes adding Heat, pyrolysis or calcining.

The method of any one of 65. embodiment 1-64 of embodiment, wherein it includes described for removing at least part liquid Liquid is exchanged with another liquid.

The method of any one of 66. embodiment 1-65 of embodiment, wherein removing at least part liquid includes liquid Extraction.

The method of any one of 67. embodiment 1-66 of embodiment further includes handling the material, forms second Material.

The method of 68. embodiment 67 of embodiment, wherein handling the hydrophobicity or hydrophilic that the material changes material Property.

The method of 69. embodiment 67 or 68 of embodiment, makes organic matter or inorganic matter exist wherein handling the material It is coated or is deposited on material surface or in material.

The method of any one of 70. embodiment 67-69 of embodiment, wherein handling the material changes material extremely The composition of a few component.

The method of any one of 71. embodiment 67-70 of embodiment, wherein handling the material makes material extremely Electronation or oxidation occur for a few component.

The method of any one of 72. embodiment 67-71 of embodiment, wherein handling the material makes material extremely Ion exchange occurs for a few component.

The method of any one of 73. embodiment 67-72 of embodiment, wherein handling the material changes material extremely The chemical structure of a few component.

The method of any one of 74. embodiment 67-73 of embodiment, wherein handling the table that the material changes material Face region.

The method of any one of 75. embodiment 67-74 of embodiment includes heating, steams wherein handling the material Hair, dehydration, hydro-thermal process, solvent heat treatment, ion heat treatment, crystallization, pyrolysis, carbon-thermal reduction, calcining or their combination.

The method of any one of 76. embodiment 1-75 of embodiment, wherein the material can be to chemical substance, biology Material, electric field, magnetic field, temperature, pressure, electromagnetic wave, mechanical force or their combination make a response.

The method of any one of 77. embodiment 1-76 of embodiment, wherein the material is porous.

The method of any one of 78. embodiment 1-77 of embodiment, wherein the material includes zeolite.

The method of any one of 79. embodiment 1-78 of embodiment, wherein the material has micropore, mesoporous, big Hole or their combination.

The material that embodiment 80. is formed by the method for any one of embodiment 1-79.

81. second material of embodiment comprising the material of embodiment 80.

82. method of embodiment comprising:

Heating and/or aging geopolymer resin material generate the first material；

Contact the first material with fluid；With

At least part fluid is removed, the second material is generated.

The method of 83. embodiment 82 of embodiment, wherein contact of first material with fluid crushes or the first material of division Material.

The method of 84. embodiment 82 or 83 of embodiment, wherein heating and/or aging geopolymer resin material packet It includes and is being lower than 100 DEG C of temperature heating and/or aging geopolymer resin material.

The method of any one of 85. embodiment 82-84 of embodiment, wherein heating and/or aging geopolymer resin Material includes heating and/or aging geopolymer resin material, and changes heating and/or aging temperature simultaneously.

The method of any one of 86. embodiment 82-85 of embodiment, wherein heating and/or aging geopolymer resin Material includes in controlled humidity heating and/or aging geopolymer resin material.

The method of any one of 87. embodiment 82-86 of embodiment, wherein heating and/or aging geopolymer resin Material is included in environmental pressure heating and/or aging geopolymer resin material.

The method of any one of 88. embodiment 82-87 of embodiment, wherein heating and/or aging geopolymer resin Material includes in the pressure no more than 2atm in closed vessel in heating and/or aging geopolymer resin material.

The method of any one of 89. embodiment 82-88 of embodiment, wherein heating and/or aging geopolymer resin Material includes heating and/or aging geopolymer resin material, without agitating resin.

The method of any one of 90. embodiment 82-89 of embodiment, wherein the first material is brittle.

The method of any one of 91. embodiment 82-90 of embodiment, wherein the first material is monolith.

The method of any one of 92. embodiment 82-91 of embodiment, wherein the first material includes particle.

The method of any one of 93. embodiment 82-92 of embodiment, wherein the first material is paste or material mud (sludge)。

The method of any one of 94. embodiment 82-93 of embodiment, wherein the first material is more more sticky than water Liquid.

The method of any one of 95. embodiment 82-94 of embodiment, wherein the first material is geopolymer.

The method of any one of 96. embodiment 82-95 of embodiment, wherein the first material has significant crystallinity.

The method of any one of 97. embodiment 82-96 of embodiment, wherein heating and/or aging geopolymer resin Material provides the significant crystallinity in the first material.

The method of any one of 98. embodiment 82-97 of embodiment, wherein the first material includes that zeolite or zeolite are multiple Condensation material.

The method of any one of 99. embodiment 82-98 of embodiment, wherein the first material includes that molecular weight is not more than The water soluble organic substance and zeolite of about 1000g/mol.

The method of any one of 100. embodiment 82-99 of embodiment, wherein the second material includes particle.

The method of any one of 101. embodiment 82-100 of embodiment, wherein the second material includes containing particle Dispersion, suspended substance, slurry or paste.

The method of 102. embodiment 100 or 101 of embodiment, wherein most of or most of particle is substantially Be made of material as described below or including material as described below: the material by particle, particle aggregate and/or The aggregation composition of grain, for the material, the particle has one or more external dimensions (more than the pact of their numbers 50% size range is 1-100nm)；And/or with the inside that size range is 1-100nm in one or more sizes Structure or surface texture；And/or has and be greater than 60m²/cm³The specific external surface area based on volume.

The method of any one of 103. embodiment 100-102 of embodiment, wherein most of or most of particle Show that bore dia is not more than the micropore of 2nm.

The method of any one of 104. embodiment 100-103 of embodiment, wherein most of or most of particle With one or more external dimensions, size range is about 0.1 μm to about 100 μm.

The method of any one of 105. embodiment 100-104 of embodiment, wherein most of or most of particle With one or more external dimensions, size range is about 100 μm to about 5000 μm.

The method of any one of 106. embodiment 100-105 of embodiment, wherein most of or most of particle With one or more external dimensions, size range is about 5mm to about 2cm.

The method of any one of 107. embodiment 82-106 of embodiment, wherein the polymer resin material includes Silicate, aluminate, aluminosilicate, organosilicate, organo-alumino-silicate, phosphate, silicophosphate, silicoaluminophosphate or Their combination.

The method of any one of 108. embodiment 82-107 of embodiment, wherein by making comprising dissolution or part The clay material of dissolution, the acidity of activated clay material or calcined clay material or alkaline solution dissolution, and the solution is hardened, To form geopolymer resin material.

The method of any one of 109. embodiment 82-108 of embodiment, wherein geopolymer resin material is a kind of Or the aqueous slkali of a variety of inorganic material, the inorganic material be selected from fumed silica, rice hull ash, silicon ash, silicate, Aluminate, aluminosilicate, organosilan, clay, mineral, metakaolin, metakaolin, activated clay, calcined clay, flying dust, Clinker, volcanic ash, burning multi-purpose waste material, glass powder and red mud.

The method of any one of 110. embodiment 82-109 of embodiment, wherein geopolymer resin material includes alkali Property substance activation or alkali activation metakaolin or metakaolin.

The method of any one of 111. embodiment 82-110 of embodiment, wherein geopolymer includes basic species The flying dust of matter activation or alkali activation.

The method of any one of 112. embodiment 82-111 of embodiment, the wherein A and aluminium of geopolymer resin material Atomic ratio be not less than 1, wherein A is any combination of alkali metal or alkali metal, and in the solution, the total amount of alkali metal ion is not The water of 1kg every lower than 5 moles.

The method of any one of 113. embodiment 82-112 of embodiment, wherein geopolymer resin material include phosphorus, Silicon, alkali metal, one or more oxides of alkaline-earth metal or hydroxide or its hydrate.

The method of any one of 114. embodiment 82-113 of embodiment, wherein geopolymer resin material include Machine silane, phosphoric acid, phosphate, hydrophosphate, organo-phosphine oxide, phosphate, silicophosphate, silicoaluminophosphate or their group It closes.

The method of any one of 115. embodiment 82-114 of embodiment, wherein making geopolymer resin material aging.

The method of any one of 116. embodiment 82-115 of embodiment, wherein geopolymer resin material includes one Kind or a variety of other components, the component independently selected from molecule, monomer, oligomer, polymer, ion, salt, biomaterial, Structure directing agent, hole template, surfactant, cluster, nano particle, particle, fiber, filler or their combination.

The method of 117. embodiment 116 of embodiment, wherein one or more other groups of geopolymer resin material Dividing includes organic matter unmixing with water.

The method of 118. embodiment 116 or 117 of embodiment, wherein geopolymer resin material is one or more Other components include the organic matter reacted with aqueous slkali, prepare one or more carboxylic acids that molecular weight is not greater than about 400 g/mol Radical ion.

The method of any one of 119. embodiment 116-118 of embodiment, wherein one kind of geopolymer resin material Or a variety of other components include the carboxylic acid ion that molecular weight is not greater than about 400g/mol.

The method of any one of 120. embodiment 116-119 of embodiment, wherein one kind of geopolymer resin material Or a variety of other components are independently selected from vegetable oil, vegetable oil, animal oil, abandoned vegetable oil, discarded animal oil, fat, biology Diesel oil, fatty acid, lipid, ester, carboxylic acid or their combination.

The method of any one of 121. embodiment 116-120 of embodiment, wherein one kind of geopolymer resin material Or a variety of other components are the carboxylic acid ions that molecular weight is not greater than about 400g/mol.

The method of any one of 122. embodiment 82-121 of embodiment, wherein the geopolymer resin material Water content is not more than 60wt%.

The method of any one of 123. embodiment 82-122 of embodiment, wherein the geopolymer resin material Water content is not more than 50wt%.

The method of any one of 124. embodiment 82-123 of embodiment, wherein the geopolymer resin material Water content is not more than 40wt%.

The method of any one of 125. embodiment 82-124 of embodiment, wherein contact packet of first material with fluid Include the contact in the first material of controlled temperature with fluid.

The method of any one of 126. embodiment 82-125 of embodiment, wherein contact packet of first material with fluid It includes in controlled temperature using the first material of fluid wash.

The method of any one of 127. embodiment 82-126 of embodiment, wherein contact packet of first material with fluid It includes in the first material of temperature heating in a fluid lower than 100 DEG C.

The method of any one of 128. embodiment 82-127 of embodiment, wherein contact packet of first material with fluid Include the first material in a fluid in controlled humidity and/or atmosphere heating.

The method of any one of 129. embodiment 82-128 of embodiment, wherein contact of first material with fluid makes First material disintegrating is at smaller piece.

The method of any one of 130. embodiment 82-129 of embodiment, wherein contact of first material with fluid makes First material splits into particle.

The method of any one of 131. embodiment 82-130 of embodiment, wherein contact packet of first material with fluid Grating (breaking) is included, pressure break (fracturing), rupture (cracking), crushes, pulverize, grinding, grinding, grinding, making Grain is crushed, crushes, smashs to pieces, suppresses or develops the first material in a fluid.

The method of any one of 132. embodiment 82-131 of embodiment, wherein contact packet of first material with fluid Stirring is included, is shaken to mixed, shears, stirring, the first material in ultrasound or oscillating fluid.

The method of any one of 133. embodiment 82-132 of embodiment, wherein contact of first material with fluid changes The composition of the composition of fluid and/or the first material.

The method of any one of 134. embodiment 82-133 of embodiment, wherein contact of first material with fluid moves In addition to one or more components of the first material.

The method of any one of 135. embodiment 82-134 of embodiment, wherein contact of first material with fluid makes One or more components dissolution of first material is in a fluid.

The method of any one of 136. embodiment 82-135 of embodiment, wherein the first material includes carboxylic acid ion, Contact of first material with fluid makes the dissolution of the carboxylic acid ion in the first material in a fluid.

The method of any one of 137. embodiment 82-136 of embodiment, wherein fluid is heated or cooled.

The method of any one of 138. embodiment 82-137 of embodiment, wherein fluid continuously flows.

The method of any one of 139. embodiment 82-138 of embodiment, wherein making fluid circulation and/or adding to fluid Pressure.

The method of any one of 140. embodiment 82-139 of embodiment, wherein fluid includes water.

The method of any one of 141. embodiment 82-140 of embodiment, wherein fluid includes steam.

The method of any one of 142. embodiment 82-141 of embodiment, wherein removal at least part fluid includes Remove the fluid of more than half amounts.

The method of any one of 143. embodiment 82-142 of embodiment, wherein removal at least part fluid includes Precipitating, decantation, filtering, centrifugation or their combination.

The method of any one of 144. embodiment 82-143 of embodiment, wherein removal at least part fluid includes Dry, spray drying, freeze-drying, evaporation, dehydration or their combination.

The method of any one of 145. embodiment 82-144 of embodiment, wherein removal at least part fluid includes Heating, pyrolysis, calcining or their combination.

The method of any one of 146. embodiment 82-145 of embodiment, wherein removal at least part fluid includes The fluid is exchanged with another fluid.

The method of any one of 147. embodiment 82-146 of embodiment, wherein removal at least part fluid includes The extraction of fluid.

The method of any one of 148. embodiment 82-147 of embodiment, wherein the second material is powder or muffin.

The method of any one of 149. embodiment 82-148 of embodiment, wherein the second material be suspended substance, slurry, Expect mud or paste.

The method of any one of 150. embodiment 82-149 of embodiment, wherein the second material includes dry particle.

The method of any one of 151. embodiment 82-150 of embodiment further includes the second material of processing, preparation the Three materials.

The method of 152. embodiment 151 of embodiment, wherein handling at least one of the second material the second material of change The chemical composition of component.

The method of 153. embodiment 151 or 152 of embodiment, wherein handling the second material changes the second material extremely The chemical structure of a few component.

The method of any one of 154. embodiment 151-153 of embodiment, wherein handling the second material changes the second material The form of material.

The method of any one of 155. embodiment 151-154 of embodiment, wherein handling the second material includes that will add Agent is added to form mixture in the second material, then spin coating, sprawl, smooth out, being sprayed, distributing, injecting, foaming, shaping, It molds, be granulated, tearing up, squeezing out or pultrusion mixture.

The method of any one of 156. embodiment 151-155 of embodiment, wherein handling the second material includes that will add Agent is added in the second material, then spin coating, sprawl, smooth out, being sprayed, distributing, injecting, foaming, shaping, molding, tearing up, squeezing Out or pultrusion mixture and in spin coating, sprawl, smooth out, be sprayed, distribute, inject, foam, shape, mold, be granulated, tear up, squeeze Mixture is heated at least part time out or during pultrusion.

The method of any one of 157. embodiment 151-156 of embodiment, wherein the form of third material is whole Material, plate, film, film, coating, line, ball, pearl, pellet, bar or their combination.

The method of any one of 158. embodiment 151-157 of embodiment, wherein third material be include organic material The composite material of material, polymer material, inorganic material, biomaterial or combinations thereof.

The method of any one of 159. embodiment 151-158 of embodiment, wherein third material be include the second material Composite material, for the second material, at least a certain proportion of hole is injected with organic material, polymer material, inorganic material Material, biomaterial or their combination.

The method of any one of 160. embodiment 151-159 of embodiment, wherein third material be include the second material Composite material, for the second material, at least a certain proportion of inner surface and/or outer surface are coated with organic material, polymerization Object material, inorganic material, biomaterial or their combination.

The method of any one of 161. embodiment 82-160 of embodiment, wherein the first material, the second material, third Material or their combination include zeolite.

The method of any one of 162. embodiment 82-161 of embodiment, wherein the first material, the second material, third Material or their any combination have micropore, mesoporous, macropore or their combination.

The material that embodiment 163. is formed by the method for any one of embodiment 82-162.

Embodiment 164. includes the first material, the second material or the third material of any one of embodiment 82-163 Material.

The method of any one of embodiment 165. embodiment 1-79 and 82-162, wherein the material, the first material, Second material or third material are substantially made of material as described below or including material as described below: the material by The aggregation of particle, the aggregate of particle, and/or particle forms, and for the material, particle has one or more external Size (about 50% size range more than their numbers is 1-100nm)；And/or there is the ruler in one or more sizes Very little range is the internal structure or surface texture of 1-100nm；And/or has and be greater than 60m²/cm³The outside based on volume compare table Area.

The material of any one of 166. embodiment 80,81,163 and 164 of embodiment, the wherein material, the first material Material, the second material or third material are substantially made of material as described below or including material as described below: the material It is made of the aggregation of particle, the aggregate of particle, and/or particle, for the material, particle has one or more outer Portion's size (about 50% size range more than their numbers is 1-100nm)；And/or have in one or more sizes Size range is the internal structure or surface texture of 1-100nm；And/or has and be greater than 60m²/cm³The external ratio based on volume Surface area.

A variety of embodiments of the present invention have been described.However, it should be understood that a variety of modifications can be carried out, and do not depart from The spirit and scope of the invention.Therefore, other embodiment is within the scope of the appended claims.

Claims

1. Methods, including:

a. Heating a geopolymer resinous material to produce a first material, wherein the geopolymeric resinous material comprises an alkali or alkaline substance activated metakaolin, metakaolinite or fly ash or selected from one or more of the following Alkaline solutions of inorganic materials of the group:

Fumed silica, rice husk ash, silica fume, silicates, aluminates, aluminosilicates, silicones, clays, minerals, pozzolans, red mud, metakaolinite, metakaolin, activated clays and calcined clay;

b. contacting the first material with a fluid, wherein the fluid comprises water; and

c. Removing at least a portion of the fluid to produce a second material, wherein contact of the first material with the fluid causes the first material to comminute into particles, and wherein the second material includes particles and is containing A dispersion, suspension, slurry or paste of particles, or it is a powder or cake.

2. The method of claim 1, wherein heating the geopolymer resin material comprises heating the geopolymer resin material at a temperature below 100°C.

3. A method according to claim 1 or 2, wherein the first material is a geopolymer material.

4. The method of any of claims 1-3, wherein the first material is a paste or slurry.

5. The method of any of claims 1-4, wherein the first material comprises a zeolite or a zeolite composite.

6. The method according to any one of claims 1-5, wherein the first material comprises a water-soluble organic matter and a zeolite having a molecular weight of not more than 1000 g/mol.

7. The method of any one of claims 1-6, wherein the geopolymer resin material comprises one or more other components independently selected from the group consisting of molecules, monomers, oligomers , polymers, ions, salts, biomaterials, structure directing agents, pore templating agents, surfactants, clusters, nanoparticles, particles, fibers, fillers, or combinations thereof, and all of the geopolymer resin materials The one or more other components include organics that react with the alkaline solution to produce one or more carboxylate ions having a molecular weight of not more than 400 g/mol.

8. The method of any one of claims 1-7, wherein the contacting of the first material with the fluid comprises stirring, shaking, shearing, agitation, sonication, or agitating the first material in the fluid.

9. The method of any one of claims 1-8, wherein the first material comprises carboxylate ions, and contact of the first material with a fluid dissolves the carboxylate ions in the first material in the fluid.

10. The method of any one of claims 1-9, wherein the second material has micropores, mesopores, macropores, or a combination thereof.

11. The method of any one of claims 1-9, wherein the fluid is water or an aqueous solution.